Impact of the dicyanomethylene substitution position on the cyclophane macrocycle formation in carbazole-based biradicals

π-Conjugated biradical compounds, featuring unique unsaturated valences and radical centers in the ground state, are fundamentally important for understanding the nature of chemical bonds and have potential applications in material science. [1] Recently, it has been demonstrated that several -conjugated mono- and biradicals systems form long strain -bonds between two unpaired electrons resulting in macrocyclic or staircase oligomers or polymers by self-assembly processes. [2] Therefore, these materials are potential building blocks for dynamic covalent chemistry (DCC) since the aggregates can be formed or broken upon soft external stimuli. For instance, 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole biradical (p-Cz-alkyl in Figure 1) reversibly converts upon soft stimuli (temperature, pressure, light) to a cyclophane tetramer as a result from the formation (or bond cleavage) of long C-C single bonds.[3] Here, we present an experimental and theoretical study in order to investigate how the N-substitution and the change from para- to meta-dicyanomethylene substitution on carbazole-based biradicals affects their biradical character and thus, their tendency to act as useful motifs for DCC (see Figure 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Analyzing Interactions of Calmodulin with HIV-1 Matrix Protein

Human immunodeficiency virus (HIV) attacks the immune system and if left untreated, could cause acquired immunodeficiency syndrome (AIDS). The HIV matrix protein (HIV-MA) is involved in replication and regulation of the HIV virus. Calmodulin (CaM), a calcium-binding protein found in all eukaryotes, has a potential role in the viral replication of HIV-MA which plays a key role in the replication of HIV. In order to investigate the interactions between calmodulin and the HIV-MA, a series of titrations with CaM are performed using circular dichroism. Circular dichroism (CD) uses circularly polarized light to observe the secondary structure of a molecule. The circularly polarized light is broken up into left and right components. When the molecule contains a chiral center, the left and right components are absorbed to different extents, and the differential absorption is measured with CD. Through a series of titrations, the chemical environment is changed in small increments so the molecule will experience conformational changes. As the conformation changes, CD is used to measure the ellipticity which provides a better understanding of the secondary structure that is a result of these chemical interactions. Since CaM plays a potential role in the viral replication of HIV-MA, CD is used to investigate the protein-protein interactions and conformational changes

An infrared integrated optic astronomical beam combiner for stellar interferometry at 3-4 microns

Integrated-optic, astronomical, two-beam and three-beam, interferometric combiners have been designed and fabricated for operation in the L band (3 - 4 microns) for the first time. The devices have been realized in titanium-indiffused, x-cut lithium niobate substrates, and on-chip electro-optic fringe scanning has been demonstrated. White light fringes were produced in the laboratory using the two-beam combiner integrated with an on-chip Y-splitter.Comment: This paper was published in Optics Express and is made available as an electronic reprint with the permission of OSA. The paper can be found at the following URL on the OSA website: http://www.opticsinfobase.org/oe. Systematic or multiple reproduction or distribution to multiple locations via electronic or other means is prohibited and is subject to penalties under la

Singular del Pezzo surfaces that are equivariant compactifications

We determine which singular del Pezzo surfaces are equivariant compactifications of G_a^2, to assist with proofs of Manin's conjecture for such surfaces. Additionally, we give an example of a singular quartic del Pezzo surface that is an equivariant compactification of a semidirect product of G_a and G_m.Comment: 14 pages, main result extended to non-closed ground field

Comprehensive biomarker analyses identifies HER2, EGFR, MET RNA expression and thymidylate synthase 5'UTR SNP as predictors of benefit from S-1 adjuvant chemotherapy in Japanese patients with stage II/III gastric cancer

Purpose: A comprehensive molecular analysis was conducted to identify prognostic and predictive markers for adjuvant S-1 chemotherapy in stage II/III Japanese gastric cancer (GC) patients and to evaluate their potential suitability for alternative cytotoxic or targeted drugs. Experimental Design: We investigated genetic polymorphisms of enzymes potentially involved in 5-fluoruracil (5-FU) metabolism as well as platinum resistance, previously identified genomic subtypes potentially predicting 5-FU benefit, and mRNA expression levels of receptor tyrosine kinases and KRAS as potential treatment targets in a single institution cohort of 252 stage II/III GC patients treated with or without S-1 after D2 gastrectomy. Results: 88% and 62% GC had a potentially 5-FU sensitive phenotype by SNP analyses of TS 3'UTR, and TS 5'UTR, respectively. 24%, 46%, 40%, 5%, and 44% GC had a potentially platinum sensitive phenotype by SNP analyses of GSTP1, ERCC1 rs11615, ERCC1 rs3212986, ERCC2, and XRCC1, respectively. High HER2, EGFR, FGFR2, or MET mRNA expression was observed in 49%, 66%, 72%, and 54% GC, respectively. High HER2 expression was the only significant prognosticator (HR=3.912, 95%CI: 1.706-8.973, p=0.0005). High HER2 (p=0.031), low EGFR (p=0.124), high MET (p=0.165) RNA expression, and TS 5'UTR subtype 2R/2R, 2R/3C, or 3C (p=0.058) were significant independent predictors for S-1 resistance. Conclusions: The present study suggests that platinum-based or RTK targeted agents could be alternative treatment options for a substantial subgroup of Japanese GC patients currently treated with S-1. HER2, EGFR, MET, and TS 5'UTR SNP appear to be promising predictive markers for S-1 resistance warranting validation in an independent GC series

Micro-Raman study of crichtonite group minerals enclosed into mantle garnet

We report the first comprehensive micro-Raman study of crichtonite group minerals (CGM) as inclusions in pyropic garnet grains from peridotite and pyroxenite mantle xenoliths of the Yakutian kimberlites as well as in garnet xenocrysts from the Aldan shield lamprophyres (Russia). The CGM form (i) morphologically oriented needles, lamellae, and short prisms and (ii) optically unoriented subhedral to euhedral grains, either single or intergrown with other minerals. We considered common mantle-derived CGM species (like loveringite, lindsleyite, and their analogues), with Ca, Ba, or Sr dominating in the dodecahedral A site and Zr or Fe in the octahedral B site. The Raman bands at the region of 600–830 cm−1 are indicative of CGM and their crystal-chemical distinction, although the intensity and shape of the bands appear to be dependent on laser beam power and wavelength. The factor-group analysis based on the loveringite crystal structure showed the octahedral and tetrahedral cation groups with 18f and 6c Wyckoff positions, namely, dominantly TiO6 and to a lower extent CrO6, MgO4, and FeO4 groups, to be the major contributors to the Raman spectral features. The ionic groups with dodecahedral (M0) and octahedral (M1) coordination are inactive for Raman scattering while active in infrared absorption. A number of observed Raman modes in the CGM spectra are several times lower than that predicted by the factor group analysis. The noticed broadening of modes in the CGM Raman spectra may result from a combining of bands at the narrow frequency shift regions. Solid solution behavior, luminescence, and partial metamictization of the CGM may exert additional influence on the Raman band shape. The Raman spectral features showed CGM to be accurately identified and distinguished from other Ti-, Fe-, Cr-, and Zr-containing oxides (e.g., ilmenite or those of spinel and magnetoplumbite groups) occurring as accessory mantle minerals. © 2020 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons LtdRussian Science Foundation, RSF: 18‐77‐10062Council on grants of the President of the Russian FederationThis study was supported by the Russian Science Foundation (Grant 18‐77‐10062). The equipment of the Ural Center for Shared Use «Modern Nanotechnology», Ural Federal University, and the Analytical Center for Multi‐elemental and Isotope Research, IGM, was used. Sampling was supported by the Russian Federation state assignment project of IGM. We are grateful to Nikolai V. Sobolev for Samples O‐173, O‐39, and O‐264. Vladimir N. Korolyuk, Elena N. Nigmatulina (IGM), and Allan Patchen (UT) are highly appreciated for the help with EMP analyses. We express our sincere thanks to F. Nestola and an anonymous reviewer for their thorough reviews and helpful suggestions, and to C. Marshall for regardful editorial handling of the manuscript on every stage of its revision

Continental flood basalts derived from the hydrous mantle transition zone

It has previously been postulated that the Earth's hydrous mantle transition zone may play a key role in intraplate magmatism, but no confirmatory evidence has been reported. Here we demonstrate that hydrothermally altered subducted oceanic crust was involved in generating the late Cenozoic Chifeng continental flood basalts of East Asia. This study combines oxygen isotopes with conventional geochemistry to provide evidence for an origin in the hydrous mantle transition zone. These observations lead us to propose an alternative thermochemical model, whereby slab-triggered wet upwelling produces large volumes of melt that may rise from the hydrous mantle transition zone. This model explains the lack of pre-magmatic lithospheric extension or a hotspot track and also the arc-like signatures observed in some large-scale intracontinental magmas. Deep-Earth water cycling, linked to cold subduction, slab stagnation, wet mantle upwelling and assembly/breakup of supercontinents, can potentially account for the chemical diversity of many continental flood basalts

Structural effects and the spin reorientation in Au/Co/Au films

n/

Environmental effects of a marine fish farm of gilthead seabream (Sparus aurata) in the NW Mediterranean Sea on water column and sediment

This study examined the effects of organic enrichment on water column, sediments and macrofauna caused by a fish farm in the Mediterranean Sea. Samples were collected on four sampling campaigns over a one-year cycle. Significant differences were found in the water column in dissolved oxygen, dissolved inorganic nitrogen, phosphate and total phosphorus concentrations between the fish farm and the control. The increase in the dissolved inorganic nitrogen and phosphate concentrations at the fish farm modified the stoichiometric ratios between nutrients, with silicate acting as limiting nutrient at the fish farm 11% more than at the control. Nevertheless, chlorophyll a concentration in the water column was higher at the control station, probably due to the fouling of the underwater fish farm structures. Significant differences were found in sediment concentrations of organic matter, total phosphorus and redox potential between the fish farm and the control. The Canonical Correlation Analysis indicated that organic matter, total phosphorus, redox potential and% of gravels accounted for 68.9% of the total variance in the species data. Changes were observed in macrofauna, with a decrease in number of species and up to a nine-fold increase in abundance with respect to the control. © 2013 Blackwell Publishing Ltd.We would like to thank the Caja del Mediterraneo (CAM) for a pre-doctoral fellowship fund for this research and Antonio Asuncion Acuigroup Maremar Manager, for the facilities and support in conducting the study. The translation of this paper was funded by the Universidad Politecnica de Valencia, Spain.Morata Higón, T.; Falco Giaccaglia, SL.; Gadea, I.; Sospedra Ciscar, J.; Rodilla Alamá, M. (2013). Environmental effects of a marine fish farm of gilthead seabream (Sparus aurata) in the NW Mediterranean Sea on water column and sediment. 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G., Black, K., Bodoy, A., Emblow, C., Fernandes, T. F., … Angel, D. (2009). Assessing the suitability of a range of benthic indices in the evaluation of environmental impact of fin and shellfish aquaculture located in sites across Europe. Aquaculture, 293(3-4), 231-240. doi:10.1016/j.aquaculture.2009.04.037Braeckman, U., Provoost, P., Gribsholt, B., Van Gansbeke, D., Middelburg, J., Soetaert, K., … Vanaverbeke, J. (2010). Role of macrofauna functional traits and density in biogeochemical fluxes and bioturbation. Marine Ecology Progress Series, 399, 173-186. doi:10.3354/meps08336Chou, C. L., Haya, K., Paon, L. A., Burridge, L., & Moffatt, J. D. (2002). Aquaculture-related trace metals in sediments and lobsters and relevance to environmental monitoring program ratings for near-field effects. Marine Pollution Bulletin, 44(11), 1259-1268. doi:10.1016/s0025-326x(02)00219-9Christensen, P., Rysgaard, S., Sloth, N., Dalsgaard, T., & Schwærter, S. (2000). 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(1997). Environmental risk from dissolved ivermectin to marine organisms. Aquaculture, 158(3-4), 263-275. doi:10.1016/s0044-8486(97)00209-3Dean, R. J., Shimmield, T. M., & Black, K. D. (2007). Copper, zinc and cadmium in marine cage fish farm sediments: An extensive survey. Environmental Pollution, 145(1), 84-95. doi:10.1016/j.envpol.2006.03.050Delgado, O., Ruiz, J., Pérez, M., Romero, J., & Ballesteros, E. (1999). Effects of fish farming on seagrass (Posidonia oceanica) in a Mediterranean bay: seagrass decline after organic loading cessation. Oceanologica Acta, 22(1), 109-117. doi:10.1016/s0399-1784(99)80037-1Dell’Anno, A., Mei, M. ., Pusceddu, A., & Danovaro, R. (2002). Assessing the trophic state and eutrophication of coastal marine systems: a new approach based on the biochemical composition of sediment organic matter. Marine Pollution Bulletin, 44(7), 611-622. doi:10.1016/s0025-326x(01)00302-2Ferrón, S., Ortega, T., & Forja, J. M. (2009). 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