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.

Formation of Fullerooxazoles from C61HPh3-: The Regioselectivity of Heteroatom Additions

The formation of fullerooxazoles from C61HPh3- has been examined in benzonitrile (PhCN), m-methoxybenzonitrile (m-OCH3PhCN), m-tolunitrile (m-CH3PhCN), and o-tolunitrile (o-CH3PhCN), where cis-1 bisadducts wit h Ph-, m-OCH3Ph-, m-CH3Ph-, and o-CH3Ph-substituted cyclic imidate next to the phenylmethano are formed its evidenced by various characterizations. Interestingly, only regioisomers 2a-d with the oxygen atom bonded to C4/C5 and the nitrogen atom bonded to C3/C6 are generated its demonstrated by heteronuclear multiple bond coherence (HMBC) NMR, while the alternative regioisomers 3a-d, which have the oxygen and nitrogen atoms at C3/C6 and C4/C5, respectively, are not formed from the reactions, even though the DFT (density functional theory) calculations have predicted that the energy differences between the two types of regioisomers are very small, with regioisomers 3a-d actually having lower energies than 2a-d The results are rationalized by the charge distributions Of C61HPh3-, where computational calculations have shown that the negative charges on C4 and C5 are greater than those on C3 and C6, indicating that the exhibited site selectivity of heteroatoms is a result of the charge-directed addition process

Chromosomal aberrations induced by C-12(6+) ions and Co-60 gamma-rays in mouse immature oocytes

The ovaries of Kun-Ming strain mice (3 weeks) were irradiated with different doses of C-12(6+) ion or Co-60 gamma-ray. Chromosomal aberrations were analyzed in metaphase II oocytes at 7 weeks after irradiation. The relative biological effectiveness (RBE) of C C-12(6+) ion was calculated with respect to Co-60 gamma-ray for the induction of chromosornal aberrations. The C-12(6+) ion and Co-60 gamma-ray dose-response relationships for chromosomal aberrations were plotted by linear quadratic models. The data showed that there was a dose-related increase in frequency of chromosomal aberrations in all the treated groups compared to controls. The RBE values for C-12(6+) ions relative to (CO)-C-60 gamma-rays were 2.49, 2.29, 1.57, 1.42 or 1.32 for the doses of 0.5, 1.0, 2.07 4.0 or 6.0 Gy, respectively. Moreover, a different distribution of the various types of aberrations has been found for C-12(6+) ion and Co-60 gamma-ray irradiations. The dose-response relationships for C-12(6+) ion and (CO)-C-60 gamma-ray exhibited positive correlations. The results from the present study may be helpful for assessing genetic damage following exposure of immature oocytes to ionizing radiation.

Structures, Stabilities and Strain in C60 and C70 Derivatives Fullerenes, Nanotubes and Carbon Nanostructures

The stabilities of a number of small adducts as well as larger hydrides of C-60 and C-70 are reported using semiempirical MO methods. The data are shown to be consistent with the nature of bond alternation in the parent fullerenes and strain effects in the cage systems.

Preliminary observations on the effect of a. c. current on Catla catla and Ophicephalus punctatus

In order to evolve suitable electrical fishing gear for inland waters, preliminary experiments have been conducted to observe effect of a. c. currents on Catla catla at voltages of 30, 90 and 120, pH 7.3 and 8.4, temperature 48°F, 78°F and 105°F, distance between electrodes 25 cm, 50 cm and 75 cm, size range of fish 100 mm, to 235 mm. Apparatus used was a 5 kw; a. c. 60 cycles generator with resistance control. Larger sizes of fish were more prone to electric shock. Higher temperature increases the intensity of the shock, while variation of pH between 7.3 to 8.4 did not materially affect the intensity of the shock. Fishing with a mixed population of Catla catla and Ophicephalus punctatus gave a greater percentage of mortality for the latter.

纳秒激光诱导C60分子碎裂中轻碎片离子C+n(n＜30)的产生机理研究

The time of flight mass spectrometric technique was used to determine the initial mean kinetic energy of small fragment ions C-n(+) (n <= 11) produced from C-60 excited by 532 nm nanosecond laser pulses. The measured kinetic energy shows little variation with the fragment mass and the laser fluence in a broad range. Based on the assumption that C-30(+) is produced predominantly by a single electron emission followed by successive C-2 evaporation from hot C-60 in the nanosecond laser field, the formation of small fragments is interpreted as the complete breakup of the unstable C-30(+) cage structure. The interpretation is consistent with the previously observed results.

Polymeric fullerene oxide films produced by decomposition of hexanitro[60]fullerene

A new poly(fullerene oxide) thin film material has been fabricated by thermal activation and electron bombardment on hexanitro[60]fullerene (HNF) film deposited on a An substrate, all under vacuum conditions. The reaction products in the polymerization process are analyzed by XPS, UPS, IR, TGA-MS and LDI-MS techniques. It is found that the main effect of thermal and radiation treatments is to induce cleavage of -NO bonds from HNF molecules resulted in the release of nitric oxide gas and the formation of fullerene-bound oxyradicals, C-60-C-6. Spectroscopic evidence strongly suggests that rearrangement of fullerenic nitro moieties into nitrito groups is involved in the HNF decomposition process prior to the generation of reactive oxyradical intermediates. Consequently, the intermolecular coupling reaction of these oxyradicals leads to carbon polymer networks containing oxygen-bridged fullerenes. The thermally generated polymeric thin film is stable up to 900 K. Electron bombardment is also effective in both the decomposition of -NO2 groups and the removal of -OH groups present in HNF films. UV irradiation at 365 nm alone is shown to be not as efficient for the polymer formation. (C) 2003 Elsevier Ltd. All rights reserved.

C-118 from fullerenols: Formation, structure and intermolecular nC(2) transfer reactions in mass spectrometry

In fast atom bombardment, two fullerenols C-60(OH)(x) (x=13-15) and C-60(OH)(x) (x-24-26) gave rise to a group of ions centered at C-118 with intervals of 24 mass units in the high mass region. In contrast, no such ions appeared in the mass spectra of pure C-60, C-70 and other fullerene derivatives such as C-60(C6H5)(10), under the same conditions. It is proposed that the pinacol rearrangement of C-60(OH)(2), resulting from partial rupture of the polyhydroxy molecules, produces C-59 with two carbon atoms bearing an unpaired electron, and that dimerization of this reactive intermediate is responsible for the formation of the predominant product C-118. An intermolecular nC(2) transfer process is used to explain the symmetrical abundance distribution of these product ions in the spectra of fullerenols.

Miscibility, crystallization, and morphology studies of thermosetting polyimide PMR-15/PEK-C blends

Miscibility, crystallization, and mechanical properties of blends of thermosetting polyimide PMR-15 and phenolphthalein poly(ether ketone) (PEK-C) were examined. With the exception of the 90/10 blend, which has two glass transition peaks, all the blends with PMR-15 less than 90 wt % are miscible in the amorphous state according to DMA results. Addition of PEK-C hindered significantly the crystallization of PMR-15, indicating that there must exist some kind of interaction between molecular chains of PMR-15 and those of PEK-C. The semi-IPN system of PMR-15/PEK-C blends exhibits good toughness. Two distinct microphases, interweaving at the phase boundaries, were found in the PMR-15/PEK-C 60/40 blend. The toughness effect of the blends is discussed in terms of the interface adhesion between the two distinct phases and the domain sizes of the phases. The relation between miscibility and toughness of the blends was investigated. (C) 1996 John Wiley & Sons, Inc.

C_(60)与某些有机小分子的气相离子-分子反应

气相C_(60)在化学电离质谱中分别与3种氯代甲烷和4种氯代乙烷的分子离子及其碎片离子发生气相离子-分子反应,观察到C_(60)的几十种气相加合离子(其中绝大多数为含氯原子的).通过对比分析认为,C_(60)的加合离子丰度并不与反应物氯代烷中相应碎片离子丰度成顺变关系,某些含自由基的碎片离子(或自由基)与C_(60)(或C~+-(60))表现出更强的反应活性,这体现了C_(60)作为烯烃的吸自由基特性.

Early development of Costaria costata (C. Agardh) Saunders and cultivation trials

Costaria costata (C. Agardh) Saunders is one of common kelps distributed in many coastal areas worldwide; however, in China, no reports have been made on cultivation of the genus. To investigate potential cultivation of the species in the northern part of China, trials on isolation and preservation of the gametophytes were conducted using C. costata from Korea; growth and development of the gametophytes were observed. We showed that at 10 +/- 1A degrees C, 60 mu mol m(-2)s(-1) and 12:12 h (L:D), freshly released zoospores settled down within 1 hour, and then developed into the primary cell during the following 2 days. After a vegetative growth phase lasting 6-8 days, female gametophytes became 3-4 times larger in diameter than that of the primary cell, but still remained at a unicellular stage, while male gametophytes divided into 4-10 cells with only a slight change in size. Fertilization occurred within 10 days after the zoospores were released from the sporangia, and the apical and basal tissues of the juvenile sporophyte divided and differentiated into the blade and stipe. Temperature and irradiance influenced gametophytic vegetative growth and developmental patterns. Generally, low irradiance (15 mu mol m(-2)s(-1) and 30 mu mol m(-2)s(-1)) was unfavorable to the induction of fertility, but it enhanced female gametophyte division. The optimal conditions for vegetative growth were 15A degrees C and 30 mu mol m(-2)s(-1). After transplantation of the juvenile seedlings and after eight months cultivation, the harvested mature blade reached 194 cm in length and 32.7 cm in width. Our study proves that it is feasible to implement propagation and large scale cultivation of C. costata in northern China.

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.