Lattice-matched versus lattice-mismatched models to describe epitaxial monolayer graphene on Ru (0001)

Monolayer graphene grown on Ru(0001) surfaces forms a superstructure with periodic modulations in its geometry and electronic structure. The large dimension and inhomogeneous features of this superstructure make its description and subsequent analysis a challenge for theoretical modeling based on density functional theory. In this work, we compare two different approaches to describe the same physical properties of this surface, focusing on the geometry and the electronic states confined at the surface. In the more complex approach, the actual moiré structure is taken into account by means of large unit cells, whereas in the simplest one, the graphene moiré is completely neglected by representing the system as a stretched graphene layer that adapts pseudomorphically to Ru(0001). As shown in previous work, the more complex model provides an accurate description of the existing experimental observations. More interestingly, we show that the simplified stretched models, which are computationally inexpensive, reproduce qualitatively the main features of the surface electronic structure. They also provide a simple and comprehensive picture of the observed electronic structure, thus making them particularly useful for the analysis of these and maybe other complex interfacesWe thank Barcelona Supercomputing Center–Spanish Supercomputing Network (BSC-RES) and Centro de Computación Científica – Universidad Autónoma de Madrid (CCC-UAM) for allocation of computer time. Work supported by the MICINN Projects No. FIS2010-15127, No. FIS2010-18847, No. CTQ2010-17006, No. FIS-2010-19609- C09-00, No. ACI2008-0777, No. 2010C-07-25200, and No. CSD2007-00010, the CAM program NANOBIOMAGNET S2009/MAT1726 and the Gobierno Vasco-UPV/EHU Project No. IT-366-07. S.B. acknowledges financial support from MEC under FPU Grant No. AP-2007-00157. D.S. acknowledges financial support from the FPI-UAM grant progra

Role of dispersion forces in the structure of graphene monolayers on Ru surfaces

Elaborate density functional theory (DFT) calculations that include the effect of van der Waals (vdW) interactions have been carried out for graphene epitaxially grown on Ru(0001). The calculations predict a reduction of structural corrugation in the observed moiré pattern of about 25% (∼0.4  Å) with respect to DFT calculations without vdW corrections. The simulated STM topographies are close to the experimental ones in a wide range of bias voltage around the Fermi levelWe thank Mare Nostrum BSC and CCC-UAM for computer time. Work supported by the MICINN projects FIS2010-15127, FIS2010-18847, CTQ2010-17006, FIS2010-19609-C02-00, ACI2008-0777, 2010C-07- 25200, and CSD2007-00010, the CAM program NANOBIOMAGNET S2009/MAT1726, and the Gobierno Vasco—UPV/EHU project IT-366-0

Electron localization in epitaxial graphene on Ru(0001) determined by moiré corrugation

The interpretation of scanning tunneling spectroscopy (STS) and scanning tunneling microscopy measurements of epitaxial graphene on lattice-mismatched substrates is a challenging problem, because of the spatial modulation in the electronic structure imposed by the formation of a moiré pattern. Here we describe the electronic structure of graphene adsorbed on Ru(0001) by means of density functional theory calculations that include van der Waals interactions and are performed on a large 11×11 unit cell to account for the observed moiré patterns. Our results show the existence of localized electronic states in the high and low areas of the moiré at energies close to and well above the Fermi level, respectively. Localization is due to the spatial modulation of the graphene-Ru(0001) interaction and is at the origin of the various peaks observed in STS spectraWork supported by the MICINN Projects No. FIS2010-15127, No. FIS2010-18847, No. CTQ2010-17006, No. FIS-2010-19609-C09-00, No. ACI2008-0777, No. 2010C-07-25200, and No. CSD2007-00010, the CAM program NANOBIOMAGNET S2009/MAT1726, and the Gobierno Vasco-UPV/EHU Project No. IT-366-07. S.B. acknowledges financial support from MEC under FPU Grant No. AP-2007-0015

Expression of a carotenoid‐modifying gene and evolution of red coloration in weaverbirds (Ploceidae)

Red carotenoid colours in birds are widely assumed to be sexually selected quality indicators, but this rests on a very incomplete understanding of genetic mechanisms and honesty-mediating costs. Recent progress was made by the implication of teh gene CYP2J19 as an avian carotenoid ketolase, catalysing the synthesis of red C4-ketocarotenoids from yellow dietary precursors, and potentially a major mechanism behind red coloration in birds. Here we investigate the role of CYP2J19 in the spectacular colour diversification of African weaverbirds (Ploceidae), represented by five genera and 16 species: eight red, seven yellow, and one without carotenoid coloration. All species had a single copy of CYP2J19, unlike the duplication found in the zebra finch, with high expression in the retina, confirming its function in coloring red oil droplets. Expression was weak or undetected in skin and follicles of pigment-depositing feather buds, as well as in beaks and tarsi, including those of the red-billed quelea. In contrast, the hepatic (liver) expression of CYP2J19 was consistenly higher (>14 fold) in seven species with C4-ketocarotenoid coloration than in species without (including one red species), an association strongly supported by a phylogenetic comparative analysis. The results suggest a critical role of the candidate ketolase, CYP2J19, in the evolution of red C4-ketocarotenoid colour variation in ploceids. Since ancestral state reconstruction suggests that ketocarotenoid coloration has evolved twice in this group (once in Euplectes and once in the Quelea/Foudia clade), we argue that while CYP2J19 has retained its ancestral role in the retina, it has likely been co-opted for red coloration independently in the two lineages, via increased hepatic expression

Carotenoid content and reflectance of yellow and red nuptial plumages in widowbirds (Euplectes spp.)

1. Ornamental carotenoid coloration is commonly based on several different pigments with different nutritional and metabolic constraints. The identification and quantification of carotenoid pigments is therefore crucial to the understanding of signal content and signal evolution. 2. In male widowbirds (Euplectes spp.), the striking yellow and red carotenoid colours have been measured by reflectance spectrometry and studied with respect to sexual selection through male contest competition, but their biochemical mechanisms have not been analysed. 3. Here we use reflectance analysis and high performance liquid chromatography (HPLC) to describe the species-specific colours and plumage carotenoids in three widowbird species: yellow-mantled widowbird (YMW) Euplectes macrourus, red-shouldered widowbird (RSW) E. axillaris and red-collared widowbird (RCW) E. ardens. 4. YMW yellow (‘hue’ colorimetric λR50 = 522 nm) derives from the two ‘dietary yellow’ xanthophylls lutein and zeaxanthin, together with small amounts of ‘derived yellow’ pigments (3′-dehydrolutein and canary xanthophylls). 5. RCW red (λR50 = 574 nm) is achieved by the addition of low concentrations of ‘derived red ’ 4-keto-carotenoids, notably α- and β-doradexanthin and canthaxanthin. 6. RSW red (λR50 = 589 nm) is, in contrast, created by high concentrations of ‘dietary yellow ’ pigments (lutein, zeaxanthin) and ‘derived yellow ’ anhydrolutein, the latter only recently described in birds. 7. The two different mechanisms of producing red plumage are compared with other bird species and discussed with regard to costs and signal ‘honesty’

Differential effects of testosterone, dihydrotestosterone and estradiol on carotenoid deposition in an avian sexually selected signal

Recent studies have demonstrated that carotenoid-based traits are under the control of testosterone (T) by up-regulation of carotenoid carriers (lipoproteins) and/or tissue-specific uptake of carotenoids. T can be converted to dihydrotestosterone (DHT) and estradiol (E2), and variation in conversion rate may partly explain some contradictory findings in the literature. Moreover, most studies on the effect of T on sexual signals have focused on the male sex only, while in many species females show the same signal, albeit to a lesser extent. We studied the effects of T, DHT, and E2 treatment in male and female diamond doves Geopelia cuneata in which both sexes have an enlarged red eye ring, which is more pronounced in males. We first showed that this periorbital ring contains very high concentration of carotenoids, of which most are lutein esters. Both T and DHT were effective in enhancing hue, UV-chroma and size in both sexes, while E2 was ineffective. However, E2 dramatically increased the concentration of circulating lipoproteins. We conclude that in both sexes both color and size of the secondary sexual trait are androgen dependent. The action of androgens is independent of lipoproteins regulation. Potential mechanisms and their consequences for trade-off are discussed

Reaction of N-haloamidines with 1,1-diaminoethenes

In the context of our work on the synthesis of imidazole ring system we have studied the reaction beetween N-haloamidines and 1,1-diaminoethenes

European Colloquium on Heterocyclic Chemistry

The reaction beetween N-haloamidines and 1,1-diaminoethenes gave 1,2-diaryl-4-amino-5-chloroimidazoles. The 1,2-diaryl-4-aminoimidazoles were obtained by reduction of the corresponding 5-chloroderivatives