63,872 research outputs found
Bauhinia bassacensis var. nicobarica Tiwari U. L., K. Ravikumar & N. Balachandran 2013, var. nov.
No full textBauhinia bassacensis var. nicobarica Tiwari U.L., K. Ravikumar & N. Balachandran, var. nov. (Figs. 1 & 2) Differs from the typical variety in having exstipulate leaves, lobes of leaves obtuse at apex, bract rusty tomentose and ovate, bracteoles 2, lanceolate, rusty tomentose; fertile stamens always 2; filaments hairy, anther lobes brown. Type:— INDIA. Great Nicobar Island: Near Army land, Campbell Bay, 20 February 2013, N- 71 o 2’ 2.9’’, E 93 o 55’ 2.9’’, 16 m ASL, K . Ravikumar, N. Balachandran and Umeshkumar Tiwari 115533 (holotype FRLH!; isotypes FRLH!, PBL!). Large, woody, climbers; tendrils coiled stout, glabrous; young branches rusty tomentose, mature grooved and lenticellate. Leaves exstipulate; petioles glabrescent, 2 7 cm long; lamina ovate-cordate, ca. 19 × 13 cm, 9 13-nerved, bifid, down to 3.5 4.8 cm length with narrow sinus, apex of lobes obtuse, base cordate, upper surface glabrous, lower brownish tomentose to glabrescent, base of the lamina with two distinct glands expanding up to pulvinous base. Inflorescences lateral or terminal, many-flowered, racemes or panicles; peduncles rusty tomentose; pedicels ca. 3.5 cm long in flower and ca. 7 cm long in fruit; bracts ovate, rusty tomentose, ca. 0.5 mm long; bracteoles 2, lanceolate, inserted near the middle of the pedicels, rusty tomentose, 1–1.5 mm long. Buds ovoid, rusty tomentose, 4–6 mm long. Hypanthium c. 1 mm long. Calyx during anthesis splitting into 2 segments forming right angles with the pedicels, 5–7 mm long, sometime persistent with fruit. Petals 2 above and three below, pubescent, creamish with purplish-red veins prominent on both sides, blade deltoid, crumpled, subequal, narrowly ovate to suborbicular with undulate margin, ca. 6 × 5 mm; claw 1.5–2 cm long, soft hairy. Stamens 9 (2 + 7); fertile stamens 2, staminodes absent sometime 1; filaments 1.2–1.6cm long, hairy; anthers 1–2 mm long, lobes brown; reduced stamens 7 in number, unequal, 3–9 mm long, filiform, white. Carpels densely brownish pilose, distinctly stalked, styles 6-8 mm, hairy with a small capitate stigma. Pods rusty tomentose, 8–13 × 3–4 cm with persistent style, stalks c. 3 mm long; styles persistent in fruit. Seeds, 2–5, dark brown, flattened, oblong-orbicular, c. 1.5 × 2 cm, smooth, glabrous. Flowering & Fruiting:— From February to March. Distribution:— India: Campbell Bay, Great Nicobar Island, Andaman and Nicobar Islands. Habitat:— Liana in mixed semi-evergreen forests. Ecological status:— About three individuals confined to an area of 1 km 2 were observed during field survey. Though it qualifies to be kept under Critically Endangered (CR) category, further studies and explorations in adjacent areas are required to ascertain its actual status. Etymology:— The varietal epithet refers to the place of its collection. This new variety is allied to typical var. bassacensis and var. backeri, but differs from both markedly in having exstipulate leaves, lobes of leaves obtuse at apex, bract rusty tomentose and ovate, bracteoles 2, lanceolate, rusty tomentose; fertile stamens always 2; filaments hairy, anther lobes brown (see table 1).Published as part of Tiwari, Umeshkumar, Ravikumar, Kaliamoorthy & Balachandran, Natesan, 2013, A new variety of Bauhinia bassacensis (Leguminosae: Caesalpinioideae) from Great Nicobar Island, India, pp. 12-18 in Phytotaxa 149 (1) on pages 13-16, DOI: 10.11646/phytotaxa.149.1.2, http://zenodo.org/record/510042
Electron transfer with core-level excitations at hybrid interfaces
No full textElectron core-level spectroscopies have emerged as effective tools to investigate several aspects of the hybrid interface between organic molecules and a substrate. In particular, resonant photoemission spectroscopy can measure interfacial electron transfer times down to the femtosecond timescale. Furthermore, the strong perturbation induced by the core hole opens up the several questions on how the properties of the interface are modified, calling for a theoretical description of the core-excited system.
We adopt a theoretical framework based on density-functional theory (DFT), where the excitation is introduced explicitly in the core-level occupation of an atom in a molecule, to investigate the electronic structure and electron transfer from/to organic molecules adsorbed on metal, semimetal, and semiconducting substrates.
The perturbing potential lowers the energy of the molecular orbitals. Focusing on the lowest-unoccupied (LUMO), a filling of the core-excited LUMO* by substrate electrons may occur within the core-hole lifetime, as found for molecules on metals where the adsorption angle is also shown to influence the electron transfer rate [1,2]. In the case of a semimetal graphene substrate, a spin-polarized LUMO* pinned at the Fermi level can be determined for physisorbed molecules. In that case electron transfer would be suppressed given the low density of states of unsupported graphene at that energy, but still possible for graphene supported on a metal [3]. For molecules adsorbed on a semiconductor, the LUMO* may form a bound exciton in the gap [4]. Here, we found especially interesting to consider the influence of thermal motion on the energy-level alignment and the absorption coefficient [5,6].
References
[1] D. Cvetko, G. Fratesi, G. Kladnik, A. Cossaro, G.P. Brivio, L. Venkataraman, and A. Morgante, submitted.
[2] A. Baby, G. Fratesi, S.R. Vaidya, L.L. Patera, C. Africh, L. Floreano, G.P. Brivio, J. Phys. Chem. C 119 (2015) 3624.
[3] A. Ravikumar, A. Baby, H. Lin, G.P. Brivio, and G. Fratesi, Scientific Reports 6 (2016) 24603.
[4] G. Fratesi, C. Motta, M. I. Trioni, G. P. Brivio, and D. Sánchez-Portal, J. Phys. Chem. C 118 (2014) 8775
[5] H. Lin, G. Fratesi, S. Selçuk, G.P. Brivio, and A. Selloni, J. Phys. Chem. C, 120 (2016) 3899.
[6] M. Muller, D. Sànchez-Portal, H. Lin, G. Fratesi, G.P. Brivio, and A. Selloni, in preparation
Spectroscopic Fingerprints of sp1 Hybridized C in Surface-Grown Molecular Assemblies
No full textThe advent of on-surface chemistry and molecular self-assembly opened the way to the realization of organic materials whose lack of stability in vacuo would otherwise forbid their synthesis. Recently the on-surface coupling of the precursors has also been used to synthesize adsorbed organic systems with chemically vulnerable linear carbon chains with sp 1 hybridization [1]. A notable advantage of on-surface synthesis is that the full realm of the experimental and theoretical surface science toolbox is available for the investigation. While the method of choice for surface-supported architectures is the scanning tunneling microscope and ultimate resolution is achieved by low-T non-contact atomic force microscopy, electron core-level spectroscopy can provide an even more local probe of the electronic properties of the material. In particular, polarized near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is here suggested to discriminate sp 1 /sp 2 character in the structures. We present an ab initio study of the polarized NEXAFS spectrum of model and real sp 1 /sp 2 materials. Calculations are performed within density functional theory with plane waves and pseudopotentials, and spectra are computed by core-excited C potentials as validated by previous studies [2,3]. We evaluate the dichroism in the spectrum for ideal carbynes and highlight the main differences relative to typical sp 2 systems. We then consider a mixed polymer alternating sp 1 C 4 units with sp 2 biphenyl groups, recently synthesized on Au(111) [4], as well as other linear structures and two-dimensional networks, pointing out a spectral line shape specifically due to the the presence of linear C chains [5]. Our study suggests that the measurements of polarized NEXAFS spectra could be used to distinctly fingerprint the presence of sp 1 hybridization in surface-grown C structures. [1] Q. Sun, R. Zhang, J. Qiu, R. Liu, and W. Xu, Adv. Mater. 2018, 30, 1705630 [2] G. Fratesi, V. Lanzilotto, L. Floreano, and G. P. Brivio, J. Phys. Chem. C 2013, 117, 6632 [3] G. Fratesi, V. Lanzilotto, S. Stranges, M. Alagia, G. P. Brivio, and L. Floreano, Phys. Chem. Chem. Phys. 2014, 16, 14834 [4] Q. Sun, L. Cai, H. Ma, C. Yuan, and W. Xu, ACS Nano 2016, 10, 7023 [5] G. Fratesi, S. Achilli, N. Manini, G. Onida, A. Baby, A. Ravikumar, A. Ugolotti, G.P. Brivio, A. Milani, and C.S. Casari, Materials 2018, 11, 255
Reactivity of Alkynes with M-C Bonds generated through C-H Activation
No full textTransition metal-catalyzed C-H activation and functionalization with various coupling partners is a well-explored area of research. Among the various coupling partners used, alkynes occupy a prominent position on account of their varied reactivity. Due to their low steric demand and a high degree of unsaturation they effectively overlap with metal d-orbitals and form multiple bond-forming events giving rise to complex skeletons that are otherwise challenging to synthesize. This makes alkyne one of the most successful coupling partners in terms of the number of useful transformations. Remarkably, by changing the reaction conditions and transition-metals from 5d to 3d, the behaviors of alkynes also change. Despite enormous explorations with alkynes, there are still a lot more possible ways by which alkynes can be made to react with M-C bonds generated through C-H activation. Especially with the development of new high and low valent first-row metal catalysts, there is plenty of scope for this chemistry to evolve as one of the most explored areas of research in coming years. Therefore, a review on this topic is both timely and useful for synthetic chemists who are working in this area. In this review, we have highlighted the diverse reactivity of alkynes with various transition metals and their applications along with some of our thoughts on future prospects
Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces
No full textThe properties of novel and prospective 2D materials are dramatically influenced by the interaction with a substrate. For example, the electronic hybridization of silicene states on Ag(111) or graphene ones on Ni(111) disrupts the Dirac fermions of the freestanding layers. This calls for efficient approaches to tune the interaction strength at the interface. Here we focus on the case of graphene functionalized by organic molecules and grown on Ni(111) and on the interfacial charge transfer dynamics. This is investigated by X-ray resonant photoemission spectroscopy, that is able to measure electron transfer rates occurring within few femtoseconds, and by a theoretical framework based on density-functional theory [1,2].
We use 4,4’-bipyridine as the prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection (τ=4fs) of electrons from the substrate to the molecule adsorbed on epitaxial graphene/Ni(111), which is characterized by a strong hybridization between C and metal states. We demonstrate that this interface can be decoupled by the addition of a second layer of graphene, where the one in contact with the metal acts as a buffer layer and the one in contact with the molecule is less hybridized with Ni underneath. As a result, the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces.
[1] G. Fratesi, C. Motta, M. I. Trioni, G. P. Brivio, and D. Sánchez-Portal, J. Phys. Chem. C 118, 8775 (2014)
[2] D. Cvetko, G. Fratesi, G. Kladnik, A. Cossaro, G.P. Brivio, L. Venkataraman, and A. Morgante, Phys. Chem. Chem. Phys. 18, 22140 (2016)
[3] A. Ravikumar, G. Kladnik, M. Müller, A. Cossaro, G. Bavdek, L. Patera, D. Sánchez-Portal, L. Venkataraman, A. Morgante, G. P. Brivio, D. Cvetko, and G. Fratesi, Nanoscale 10, 8014 (2018)
Erratum to: Effect of moderate red wine intake on cardiac prognosis after recent acute myocardial infarction of subjects with Type 2 diabetes mellitus (Diabetic Medicine, (2006), 23, 9, (974-981), 10.1111/j.1464-5491.2006.01886.x)
No full textIn an article by Marfella et al, the author name C. Saron is incorrect and should be listed as C. Sardu. Therefore the correct author list is: R. Marfella, F. Cacciapuoti, M. Siniscalchi, F. C. Sasso, F. Marchese, F. Cinone, E. Musacchio, M. A. Marfella, L. Ruggiero, G. Chiorazzo, D. Liberti, G. Chiorazzo, G. F. Nicoletti, C. Sardu, F. D'Andrea, C. Ammendola, M. Verza and L. Coppola.In an article by Marfella et al, the author name C. Saron is incorrect and should be listed as C. Sardu. Therefore the correct author list is: R. Marfella, F. Cacciapuoti, M. Siniscalchi, F. C. Sasso, F. Marchese, F. Cinone, E. Musacchio, M. A. Marfella, L. Ruggiero, G. Chiorazzo, D. Liberti, G. Chiorazzo, G. F. Nicoletti, C. Sardu, F. D'Andrea, C. Ammendola, M. Verza and L. Coppola
Effect of Ru surface composition on the CO tolerance of Ru modified carbon supported Pt catalysts
No full textA series of ruthenium modified carbon supported catalysts have been prepared by surface organometallic chemistry (SOMC) with the following nominal Ru:Pt surface ratios, (1:4)RuPt/C, (1:2)RuPt/C, (3:4)RuPt/C and (1:1)RuPt/C. The catalysts were characterised using X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), cyclic voltammetry (CV), and half-cell polarisation studies. The XRD measurements showed that a bulk PtRu alloy was not formed following SONIC modification. However, the EXAFS measurements indicated that a surface alloy is formed upon electrochemical reduction of the Ru modified catalysts. The CV studies show that the electrooxidation of CO on the Ru modified Pt/C catalysts occurs at lower potentials than on the unmodified Pt/C catalysts, but at higher potentials than on an alloyed PtRu/C with a bulk composition of 1:1 Pt:Ru. Half cell polarisation measurements in 100 ppm CO in H-2 show that the CO tolerance of the SONIC RuPt/C catalysts approached that of the conventional PtRu/C alloy catalyst. The results therefore indicate that a bulk alloy phase is not an essential factor in the improvement in CO tolerance of PtRu/C catalysts over that of Pt/C
In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst
No full textThe Ru–CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.<br/
Measurement of the ratio of prompt χ c to J / ψ production in pp collisions at √s = 7 TeV
No full textThe prompt production of charmonium χ c and J / ψ states is studied in proton-proton collisions at a centre-of-mass energy of √s = 7 TeV at the Large Hadron Collider. The χ c and J / ψ mesons are identified through their decays χ c → J / ψ γ and J / ψ → μ + μ - using 36 pb - 1 of data collected by the LHCb detector in 2010. The ratio of the prompt production cross-sections for χ c and J / ψ, σ (χ c → J / ψ γ) / σ (J / ψ), is determined as a function of the J / ψ transverse momentum in the range 2 < p T J / ψ < 15 GeV / c. The results are in excellent agreement with next-to-leading order non-relativistic expectations and show a significant discrepancy compared with the colour singlet model prediction at leading order, especially in the low p T J / ψ region
Faust : Romance Of The Secret Tribunals / By George W. M. Reynolds, Author Of "The Mysteries Of London", "Pickwick Abroad", &c. Illustrated In The First Style Of The Art
No full textFAUST : ROMANCE OF THE SECRET TRIBUNALS / BY GEORGE W. M. REYNOLDS, AUTHOR OF "THE MYSTERIES OF LONDON", "PICKWICK ABROAD", &C. ILLUSTRATED IN THE FIRST STYLE OF THE ART
Faust : Romance Of The Secret Tribunals / By George W. M. Reynolds, Author Of "The Mysteries Of London", "Pickwick Abroad", &c. Illustrated In The First Style Of The Art (1)
Cover (1)
Umschlagtitel (8)
Titelseite (9)
Contents (10)
Illustrations / Prologue (11)
Prologue (12)
Chapter I.-XCV. (14)
Epilogue (119
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