Effect of triplet encapsulated atoms in [60] fullerenes: a theoretical analysis

The present investigation reports on the interaction of the C/O triplet atoms inside of the [60] fullerene (C60) species with small polar molecules (H²O, CH³OH, HF, NH³) using Density Functional Theory (DFT) calculations. The calculations show that in all the computed cases the encapuslated complexes with the molecules are more stable than without internal atoms.

Spin states of C-60(3-) and C120On- (n=2, 3, 4) anions using electron spin transient nutation spectroscopy

Electron spin transient nutation (ESTN) experiments show that the spin multiplicity of the ground state of C-60(3-) in frozen solution is a doublet with S = 1/2. In purified samples, there is no evidence for excited states or other species with higher multiplicity. In the anions Of C120On- (n = 2, 3, 4), where the CW EPR experiments have shown that a mixture of species is present, ESTN experiments confirm that a doublet with S = 1/2 is associated with the 3- anion and triplets with S = 1 are associated with the 2- and 4- anions. A weak nutation peak attributable to m(s) = -1/2 1/2 transitions within a quartet state may arise from association of anions with spins of 1/2 and 1 in solute aggregates.

Probing Charge Transfer in Benzodifuran-C-60 Dumbbell-Type Electron Donor-Acceptor Conjugates: Ground- and Excited-State Assays

Rigid electron donor-acceptor conjugates (1-3) that combine -extended benzodifurans as electron donors and C-60 molecules as electron acceptors with different linkers have been synthesized and investigated with respect to intramolecular charge-transfer events. Electrochemistry, fluorescence, and transient absorption measurements revealed tunable and structure-dependent charge-transfer processes in the ground and excited states. Our experimental findings are underpinned by density-functional theory calculations.

Gestión y análisis de riesgos aplicados al proyecto : "Remodelización del vial existente que une el municipio de Cañaveruelas (Cuenca) con el embalse de Buendía, mediante una vía de doble sentido tipo C-60 que incluye un carril bici y otro peatonal. Ordenación terrritorial en las proximidades del embalse.

El objetivo de este PFG es aplicar las herramientas de planificación a un proyecto existente y hacer un estudio del análisis de riesgos. El PFC al que se va a aplicar la gestión de riesgos es: “ Remodelación del vial existente que une el municipio de Cañaveruelas (Cuenca) con el embalse de Buendía, mediante una vía de doble sentido tipo C-60 que incluye un carril bici y otro peatonal. Ordenación territorial en las proximidades al embalse”. Fue realizado por Laura Gallego Salagre y por mí, para la defensa del PFC de Ingeniero Técnico en Topografía en junio de 2013. - Descripción breve del proyecto al que se va a aplicar la herramienta de gestión. - Estudio de los métodos y de las herramientas de gestión de análisis de los riesgos - Diseño de una planificación adecuada y eficiente. - Identificación de los riesgos que puedan afectar al proyecto - Realizar un análisis cualitativo y cuantitativo de Riesgos - Planificar las respuestas a los Riesgos - Analizar las diferentes respuestas - Comparar la planificación determinista con la realizada tras el análisis de riesgos. Para hacer un estudio del análisis de riesgos, hay que empezar por una planificación detallada del proyecto e identificar los posibles riesgos que puedan aparecer. Después haremos una estimación de los recursos y los asignaremos a las diferentes actividades. Posteriormente se realizará una red de procedencias, se calculará el camino crítico y se establecerá un plan de hitos para realizar un análisis de riesgos mediante el método Monte Carlo, que nos indicará la incertidumbre de las actividades. Posteriormente identificaremos los posibles riesgos que puedan afectar a nuestra planificación, los analizaremos cualitativa y cuantitativamente y se evaluarán las acciones de mitigación de los riesgos. Por último, se creará el impacto de estos en las actividades y a partir de ellos, se harán los calendarios pre y post mitigados para su posterior análisis.

Structural and Electrical Investigation of C 60 –Graphene Vertical Heterostructures

Graphene, with its unique electronic and structural qualities, has become an important playground for studying adsorption and assembly of various materials including organic molecules. Moreover, organic/graphene vertical structures assembled by van der Waals interaction have potential for multifunctional device applications. Here, we investigate structural and electrical properties of vertical heterostructures composed of C60 thin film on graphene. The assembled film structure of C60 on graphene is investigated using transmission electron microscopy, which reveals a uniform morphology of C60 film on graphene with a grain size as large as 500 nm. The strong epitaxial relations between C60 crystal and graphene lattice directions are found, and van der Waals ab initio calculations support the observed phenomena. Moreover, using C60-graphene heterostructures, we fabricate vertical graphene transistors incorporating n-type organic semiconducting materials with an on/off ratio above 3 × 10(3). Our work demonstrates that graphene can serve as an excellent substrate for assembly of molecules, and attained organic/graphene heterostructures have great potential for electronics applications.

Effects of hydroxyl group distribution on the reactivity, stability and optical properties of fullerenols

We investigate the impact of hydroxyl groups on the properties of C(60)(OH)(n) systems, with n = 1, 2, 3, 4, 8, 10, 16, 18, 24, 32 and 36 by means of first-principles density functional theory calculations. A detailed analysis from the local density of states has shown that adsorbed OH groups can induce dangling bonds in specific carbon atoms around the adsorption site. This increases the tendency to form polyhydroxylated fullerenes (fullerenols). The structural stability is analyzed in terms of the calculated formation enthalpy of each species. Also, a careful examination of the electron density of states for different fullerenols shows the possibility of synthesizing single molecules with tunable optical properties.

Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes

Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C-60 and C-70). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling.

Ab initio study of SO2 molecules interacting with pristine and transition metal covered fullerenes as a possible route for nanofilters

In this work, a systematic study of SO2 molecules interacting with pristine and transition metal (TM) covered C-60 is presented by means of first principles calculations. It is observed that the SO2 molecule interacts weakly with the pristine C-60 fullerene, although the resulting interaction is largely increased when the C-60 structure is covered with Fe, Mn, or Ti atoms and the SO2 Molecules are bounded through the TM atoms. The number of bounded SO2 molecules per TM atoms, in addition to the elevated binding energies per molecules, allows us to conclude that such composites can be used as a template for efficient devices to remove SO2 molecules or, alternatively, as SO2 gas sensor.

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

HDL-C concentration is related to markers of absorption and of cholesterol synthesis: Study in subjects with low vs. high HDL-C

Background: The antiatherogenic functions of high density lipoprotein (HDL-C) include its role in reverse cholesterol transport, but to what extent the concentration of HDL-C interferes with the whole-body cholesterol metabolism is unknown. Therefore, we measured markers of body cholesterol synthesis (desmosterol and lathosterol) and of intestinal cholesterol absorption (campesterol and beta-sitosterol) in healthy subjects that differ according to their plasma HDL-C concentrations. Methods: Healthy participants presented either low HDL-C (<40 mg/dl, n = 33,17 male and 16 female) or high HDL-C (>60 mg/dl, n = 33, 17 male and 16 female), BMI <30 kg/m(2), were paired according to age and gender, without secondary factors that might interfere with their plasma lipid concentrations. Plasma concentrations of non-cholesterol sterols were measured by the combined GC-MS analysis. Results: Plasma desmosterol did not differ between the two groups; however, as compared with the high HDL-C participants, the low HDL-C participants presented higher concentration of lathosterol and lower concentration of the intestinal cholesterol absorption markers campesterol and beta-sitosterol. Conclusion: Plasma concentrations of HDL, and not the activities of LCAT and CETP that regulate the reverse cholesterol transport system, correlate with plasma sterol markers of intestinal cholesterol absorption directly, and of cholesterol synthesis reciprocally. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and Photodynamic Effect of New Highly Photostable Decacationically Armed [60]- and [70]Fullerene Decaiodide Monoadducts To Target Pathogenic Bacteria and Cancer Cells

Novel water-soluble decacationically armed C-60 and C-70 decaiodide monoadducts, C-60- and C-70[>M(C3N6+C3)(2)], were synthesized, characterized, and applied as photosensitizers and potential nano-PDT agents against pathogenic bacteria and cancer cells. A high number of cationic charges per fullerene cage and H-bonding moieties were designed for rapid binding to the anionic residues displayed on the outer parts of bacterial cell walls. In the presence of a high number of electron-donating iodide anions as parts of quaternary ammonium salts in the arm region, we found that C-70[>M(C3N6+C3)(2)] produced more HO center dot than C-60[>M(C3N6+C3)(2)], in addition to O-1(2). This finding offers an explanation of the preferential killing of Gram-positive and Gram-negative bacteria by C-60[>M(C3N6+C3)(2)] and C-70[>M(C3N6+C3)(2)], respectively. The hypothesis is that O-1(2) can diffuse more easily into porous cell walls of Gram-positive bacteria to reach sensitive sites, while the less permeable Gram-negative bacterial cell wall needs the more reactive HO center dot to cause real damage.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.

Stress intensity factor threshold in dental porcelains

The stress intensity factor threshold (K(IO)) is related to the stress level at which cracks start to grow stably, causing the weakening of porcelain prostheses during their use. The values of K(IO) of seven dental porcelains (with and without reinforcing leucite crystal, KAlSi(2)O(6)) stored in air (22 degrees C, 60% relative humidity) and artificial saliva (37 degrees C) were determined by measuring the crack growth velocity of radial cracks generated at the corner of Vickers indentations. The results of K(IO) were correlated with the leucite content, fracture toughness (K(Ic)), and chemical composition of the porcelains. It was observed that K(IO) increased with the increase of leucite content (only for the leucite-based porcelains) and with the increase of K(Ic). The increase in Al(2)O(3) content or the decrease in the alkali oxide (K(2)O and Na(2)O) content of the material`s glassy matrix tended to increase the K(IO) values. Storage media (air and saliva) did not significantly affect the K(IO) of porcelains tested, indicating that the control parameter of K(IO) value was not the water content of the storage media.