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Sample records for gadolinium-containing endoedral metallofullerenes

  1. Endohedral metallofullerenes

    NASA Astrophysics Data System (ADS)

    Shinohara, H.

    2000-06-01

    Endohedral metallofullerenes (fullerenes with metal atom(s) encapsulated) are novel forms of fullerene-based materials which have attracted wide interest during the past eight years, not only in physics and chemistry but also in such interdisciplinary areas as materials and biological sciences. In this paper, advances in the production, separation (isolation) and various spectroscopic characterizations of endohedral metallofullerenes are presented in an attempt to clarify their structural, electronic and solid state properties. Endohedral metallofullerenes are normally produced by DC electric arc discharge of metal/graphite composite rods used as positive electrodes. The metallofullerenes can also be produced by the so-called laser furnace method which incorporates laser vaporization of the composite rods under high temperature (ca 1000 °C). The endohedral metallofullerenes so far produced are centred on group 2 and 3 metallofullerenes such as Sc, Y, La, Ca, Sr and Ba as well as lanthanide metallofullerenes (Ce-Lu). These metal atoms have been encapsulated in higher fullerenes, especially in C82. These metallofullerenes have easily been extracted by solvents from primary soot. By using an elaborate high-performance liquid chromatography technique, the metallofullerenes are completely purified and isolated like C60 and C70. Synchrotron x-ray diffraction, 13C NMR and ultra-high vacuum scanning tunnelling microscopy (UHV-STM) studies have revealed that metal atoms are indeed encapsulated by the carbon cage and that the metal atoms are not in the centre of the fullerene cage but very close to the carbon cage, indicating the presence of a strong metal-cage interaction. It has been revealed by electron spin resonance and also by theoretical calculations that substantial electron transfers take place from the encaged metal atom to the carbon cage: intrafullerene electron transfers. Good examples are lanthanum and yttrium metallofullerenes which have the charge states of

  2. Endohedral Metallofullerene Derivatives

    NASA Technical Reports Server (NTRS)

    Dorn, Harry C. (Inventor); Iezzi, Erick B. (Inventor); Duchamp, James (Inventor)

    2008-01-01

    Trimetallic nitride endohedral metallofullerene derivatives and their preparation are described. The trimetallic nitride endohedral metallofullerene derivatives have the general formula A(sub 3-n)X(sub n)@C(sub m)(R) where n ranges from 0 to 3, A and X may be trivalent metals and may be either rare earth metal or group IIIB metals, m is between about 60 and about 200, and R is preferably an organic group. Derivatives where the R group forms cyclized derivatives with the fullerene cage are also described.

  3. Yttrium-containing endohedral metallofullerenes: Synthesis and extraction

    NASA Astrophysics Data System (ADS)

    Churilov, G. N.; Vnukova, N. G.; Tomashevich, E. V.; Dudnik, A. I.; Glushchenko, G. A.; Dubinina, I. A.; Gulyaeva, U. E.; Mel'nikova, E. I.

    2017-08-01

    Yttrium-containing endohedral metallofullerenes are synthesized in an RF arc discharge in the helium flow with embedded Y2O3. It is shown that the formation of the metallofullerenes depends on the helium pressure in a chamber; however, this dependence cannot be explained using the model of formation of conventional fullerenes without a guest atom in a molecule. The results of extraction of Y@C82 by pyridine and carbon disulfide are reported. The pressure corresponding to the maximum yttrium-containing endohedral metallofullerene content is shown to be 60 kPa; under this pressure, extraction by carbon disulfide allows obtaining 27.1 wt % of the endohedral metallofullerene, while extraction by pyridine yields its amount of 17.3 wt %.

  4. Molecular magnetic switch for a metallofullerene

    PubMed Central

    Wu, Bo; Wang, Taishan; Feng, Yongqiang; Zhang, Zhuxia; Jiang, Li; Wang, Chunru

    2015-01-01

    The endohedral fullerenes lead to well-protected internal species by the fullerene cages, and even highly reactive radicals can be stabilized. However, the manipulation of the magnetic properties of these radicals from outside remains challenging. Here we report a system of a paramagnetic metallofullerene Sc3C2@C80 connected to a nitroxide radical, to achieve the remote control of the magnetic properties of the metallofullerene. The remote nitroxide group serves as a magnetic switch for the electronic spin resonance (ESR) signals of Sc3C2@C80 via spin–spin interactions. Briefly, the nitroxide radical group can ‘switch off’ the ESR signals of the Sc3C2@C80 moiety. Moreover, the strength of spin–spin interactions between Sc3C2@C80 and the nitroxide group can be manipulated by changing the distance between these two spin centres. In addition, the ESR signals of the Sc3C2@C80 moiety can be switched on at low temperatures through weakened spin–lattice interactions. PMID:25732144

  5. Structural change of metallofullerene: an easier thermal decomposition.

    PubMed

    Zhao, Shixiong; Zhang, Jun; Guo, Xihong; Qiu, Xiaohui; Dong, Jinquan; Yuan, Bingkai; Ibrahim, Kurash; Wang, Jiaou; Qian, Haijie; Zhao, Yuliang; Yang, Shangyuan; Hao, Jian; Zhang, Hong; Yuan, Hui; Xing, Gengmei; Sun, Baoyun

    2011-10-05

    We have studied for the first time the structural change of high-purity metallofullerene (Gd@C(82)) upon heat treatment in an ultra-high vacuum system (10(-10) Torr) and examined the decomposition product through successive analysis with MS, IR, Raman, TEM, EDS and XPS. It was found that metallofullerene (Gd@C(82)) had fully collapsed at 580 °C which was lower than that for the complete destruction of C(60). The easier decomposition should be ascribed to the encapsulated metal in the carbon cage which could induce the deformation of the C-C bond. The analysis indicated that the broken metallofullerene (Gd@C(82)) became a kind of graphite-like material with a lot of defects. The Gd atoms leaked out from the carbon cage and aggregated together to form a regular arrangement.

  6. Structural change of metallofullerene: an easier thermal decomposition

    NASA Astrophysics Data System (ADS)

    Zhao, Shixiong; Zhang, Jun; Guo, Xihong; Qiu, Xiaohui; Dong, Jinquan; Yuan, Bingkai; Ibrahim, Kurash; Wang, Jiaou; Qian, Haijie; Zhao, Yuliang; Yang, Shangyuan; Hao, Jian; Zhang, Hong; Yuan, Hui; Xing, Gengmei; Sun, Baoyun

    2011-10-01

    We have studied for the first time the structural change of high-purity metallofullerene (Gd@C82) upon heat treatment in an ultra-high vacuum system (10-10 Torr) and examined the decomposition product through successive analysis with MS, IR, Raman, TEM, EDS and XPS. It was found that metallofullerene (Gd@C82) had fully collapsed at 580 °C which was lower than that for the complete destruction of C60. The easier decomposition should be ascribed to the encapsulated metal in the carbon cage which could induce the deformation of the C-C bond. The analysis indicated that the broken metallofullerene (Gd@C82) became a kind of graphite-like material with a lot of defects. The Gd atoms leaked out from the carbon cage and aggregated together to form a regular arrangement.

  7. Frequency and severity of acute allergic-like reactions to gadolinium-containing i.v. contrast media in children and adults.

    PubMed

    Dillman, Jonathan R; Ellis, James H; Cohan, Richard H; Strouse, Peter J; Jan, Sophia C

    2007-12-01

    The purpose of our study was to determine the frequency and severity of acute allergic-like reactions to i.v.-administered gadolinium-containing contrast media in children and adults. Pediatric (younger than 19 years) and adult department of radiology contrast material reaction forms involving patients who experienced acute allergic-like reactions to gadolinium-containing contrast media from January 1, 2001, through December 31, 2006, were retrospectively evaluated for the specific types of acute allergic-like reactions, reaction management, and patient outcomes. Relevant patient medical information, including documentation of prior gadolinium- or iodine-containing contrast material reaction, premedication before acute allergic-like reaction to i.v. gadolinium-containing contrast material, previous allergic reactions to substances other than contrast media, and history of asthma, was obtained by reviewing electronic medical records. Seventy-eight thousand three hundred fifty-three (65,009 adult and 13,344 pediatric) i.v. administrations of gadolinium-containing contrast material were performed during the study period. Acute allergic-like reactions were documented after 54 injections (reaction frequency, 0.07%). Forty-eight reactions involved adult patients (adult reaction frequency, 0.07%), and six reactions occurred in pediatric patients (pediatric reaction frequency, 0.04%). Forty (74%) acute allergic-like reactions were mild, 10 (19%) were moderate, and four (7%) were severe. No gadolinium-containing contrast material-related death occurred during the study period. Twenty-six (50%) of 52 patients had one or more presumed risk factors for contrast material reaction. Adult and pediatric acute allergic-like reactions to i.v.-administered gadolinium-containing contrast media are rare. Most of these reactions are mild; however, moderate and severe reactions that require immediate management do occur.

  8. Investigation of the neutron activation of endohedral rare earth metallofullerenes

    SciTech Connect

    Shilin, V. A. Lebedev, V. T.; Kolesnik, S. G.; Kozlov, V. S.; Grushko, Yu. S.; Sedov, V. P.; Kukorenko, V. V.

    2011-12-15

    Endohedral lanthanide metallofullerenes and their water-soluble biocompatible derivatives have been synthesized. The effect that fast-neutron irradiation has on the stability and nuclear physical properties of endohedral metallofullerenes that are used as magnetocontrast materials ({sup 46}Sc, {sup 140}La, {sup 141}Nd, {sup 153}Sm, {sup 152}Eu, {sup 154}Eu, {sup 153}Sm, {sup 160}Tb, {sup 169}Yb, {sup 170}Tm (isomers I and III), and {sup 177}Lu) is studied. Our hypothesis, according to which carbon-shell relaxation is based on the fast nonradiative processes of an electron shake-off type, is confirmed.

  9. Biomedical Activities of Endohedral Metallofullerene Optimized for Nanopharmaceutics

    PubMed Central

    Meng, Jie; Wang, Dong-liang; Wang, Paul C.; Jia, Lee; Chen, Chunying; Liang, Xing-Jie

    2011-01-01

    Endohedral metallofullerenes, a novel form of carbon-related nanomaterials, currently attract wide attention for their potential applications in biomedical fields such as therapeutic medicine. Most endohedral metallofullerenes are synthesized using C60 or higher molecular weight fullerenes because of the limited interior volume of fullerene. It is known that the encapsulated metal atom has strong electronic interactions with the carbon cage in metallofullerenes. Gd@C82 is one of the most important molecules in the metallofullerene family, known as Magnetic Resonance Imaging (MRI) contrast agent candidate for diagnostic imaging. Gadolinium endohedral metallofullerenol (e.g., Gd@C82(OH)22) is a functionalized fullerene with gadolinium trapped inside carbon cage. Our group previously demonstrated that the distinctive chemical and physical properties of Gd@C82(OH)22 are dependent on the number and position of the hydroxyl groups on the fullerene cage. The present article summarizes our latest findings of biomedical effects of Gd@C82(OH)22 and gives rise to a connected flow of the existing knowledge and information from experts in the field. It briefly narrates the synthesis and physico-chemical properties of Gd@C82(OH)22. The polyhydroxylated nanoparticles exhibit the enhanced water solubility and high purity, and were tested as a MRI contrast agent. Gd@C82(OH)22 treatment inhibited tumor growth in tumor-bearing nude mice. Although the precise mechanisms of this action are not well defined, our in vitro data suggest involvements of improved immunity and antioxidation by Gd@C82(OH)22 and its size-based selective targeting to tumor site. The review critically analyzed the relevant data instead of fact-listing, and explained the potential for developing Gd@C82(OH)22 into a diagnostic or therapeutic agent. PMID:21121373

  10. Bottom-up formation of endohedral mono-metallofullerenes is directed by charge transfer

    NASA Astrophysics Data System (ADS)

    Dunk, Paul W.; Mulet-Gas, Marc; Nakanishi, Yusuke; Kaiser, Nathan K.; Rodríguez-Fortea, Antonio; Shinohara, Hisanori; Poblet, Josep M.; Marshall, Alan G.; Kroto, Harold W.

    2014-12-01

    An understanding of chemical formation mechanisms is essential to achieve effective yields and targeted products. One of the most challenging endeavors is synthesis of molecular nanocarbon. Endohedral metallofullerenes are of particular interest because of their unique properties that offer promise in a variety of applications. Nevertheless, the mechanism of formation from metal-doped graphite has largely eluded experimental study, because harsh synthetic methods are required to obtain them. Here we report bottom-up formation of mono-metallofullerenes under core synthesis conditions. Charge transfer is a principal factor that guides formation, discovered by study of metallofullerene formation with virtually all available elements of the periodic table. These results could enable production strategies that overcome long-standing problems that hinder current and future applications of metallofullerenes.

  11. Two-dimensional coalescence dynamics of encapsulated metallofullerenes in carbon nanotubes.

    PubMed

    Allen, Christopher S; Ito, Yasuhiro; Robertson, Alex W; Shinohara, Hisanori; Warner, Jamie H

    2011-12-27

    We report on the coalescence of a two-dimensional (2D) chain of La@C(82) metallofullerene molecules encapsulated inside a single-wall carbon nanotube (SWNT). 2D packing of metallofullerenes is known to adopt a zigzag arrangement and cause elliptical distortion to the cross-section of the SWNT host. We show that after coalescence of the metallofullerenes into an inner nanotube the carbon nanotube host returns to its original circular cross-section. This is due to a relaxation of the strain caused by the packing of the encapsulated La@C(82) molecules into the nanotube. We identify the formation of some novel but transient fullerene-based structures formed during the intermediate stages of coalescence of the La@C(82) into an inner nanotube. These results highlight the flexible nature of SWNTs and their ability to adapt their cross-sectional profile depending upon forces induced by material encapsulated within.

  12. Self-construction of core-shell structure by metallofullerene-containing polymer.

    PubMed

    Bai, Xiaojuan; Yue, Dongmei; Zhao, Shixiong; Dong, Jinquan; Yang, Limei; Ibrahim, Kurash; Wang, Jiaou; Yang, Shangyuan; Hao, Jian; Hu, Zhongbo; Sun, Baoyun

    2011-03-01

    Metallofullerene Gd@C82 offers the opportunity to produce novel and advanced polymer-based nanocomposite materials. In this work, we reported the synthesis of novel Gd@C82-containing copolymers with the optimum condition found by changing the temperature, initiator and fullerene contents of C60-PS. The developed materials, based on polystyrene, displayed unique nanostructures which were confirmed by many measurements (GPC, AFM, SEM, TGA/DSC and NEXAFS analysis). The mechanism, stability and structure of Gd@C82-containing copolymer were discussed. This approach offers a new possibility of optimizing the polymer performance with metallofullerene.

  13. Entrapping of exohedral metallofullerenes in carbon nanotubes: (CsC60)n@SWNT nano-peapods.

    PubMed

    Sun, Bao-Yun; Sato, Yuta; Suenaga, Kazutomo; Okazaki, Toshiya; Kishi, Naoki; Sugai, Toshiki; Bandow, Shunji; Iijima, Sumio; Shinohara, Hisanori

    2005-12-28

    Exohedral C60-based metallofullerenes, CsC60, have been synthesized and successfully encapsulated into single-wall carbon nanotubes (SWNTs) in high yield by reducing C60 molecules into anions. High-resolution transmission electron microscopy (HRTEM) images and in situ electron energy loss spectroscopy (EELS) indicate that Cs atoms and C60 molecules align within SWNTs as CsC60 exohedral metallofullerenes, and that the formal charge state of encaged CsC60 is expressed as Cs+1C60-1. The present peapods with the exohedral metallofullerenes provide a new insight and the possibility to fine-tune the electronic and transport properties of carbon nanotubes.

  14. Regioselective synthesis and molecular structure of the first derivative of praseodymium-containing metallofullerenes.

    PubMed

    Zhou, Qin; Li, Hui; Lian, Yongfu; Suzuki, Mitsuaki; Bao, Lipiao; Cai, Wenting; Wang, Weiwei; Nagase, Shigeru; Lu, Xing; Akasaka, Takeshi

    2014-09-07

    Regioselective cycloaddition of adamantylidene carbene to Pr@C(2v)(9)-C82 affords the first derivative of praseodymium-containing metallofullerenes. Single-crystal X-ray crystallographic data in combination with theoretical studies demonstrate that the addition is dictated by the single metal ion encapsulated inside the fullerene cage.

  15. Recent progress in the chemistry of endohedral metallofullerenes.

    PubMed

    Lu, Xing; Bao, Lipiao; Akasaka, Takeshi; Nagase, Shigeru

    2014-12-07

    Putting metal atoms or metallic clusters into fullerenes has generated a new class of hybrid molecules, defined as endohedral metallofullerenes (EMFs), possessing novel structures and fascinating properties which are different from those of empty fullerenes. In particular, it has been revealed that the chemical properties of the cage carbons of EMFs depend strongly on the nature of the internal metallic species, such as their electronic configuration, location and even motion. Since the first report describing the successful derivatization of La@C82 in 1995, great efforts have been devoted to the chemical modification of EMFs during the last two decades. Although earlier studies mainly focused on readily available species such as M@C82, M2@C80 and M3N@C80 and the related results have been systematically summarized in our previous review paper (Chem. Commun., 2011, 47, 5942-5957), recent concerns about some relatively rare EMFs have developed rapidly. Moreover, taking advantage of single crystal X-ray crystallography, we can now clearly demonstrate the mutual influences between the internal metallic species and the chemical behaviours of the surrounding cage carbons, and the addends as well. In this article, we present recent achievements in the chemical functionalization of EMFs, which were mainly published during the last four years. For consistency, we will still pay special attention to the role that the metals play in controlling the properties of the whole EMF molecules. In this review, however, we will not only focus on concrete experimental results such as X-ray crystallographic and NMR spectroscopic data but will also include computational studies which have indeed enhanced our understanding of the chemical properties of EMFs. Applicable materials based on EMFs are also mentioned but are not discussed in detail.

  16. Tuning the selectivity of Gd3N cluster endohedral metallofullerene reactions with Lewis acids.

    PubMed

    Stevenson, Steven; Rottinger, Khristina A; Fahim, Muska; Field, Jessica S; Martin, Benjamin R; Arvola, Kristine D

    2014-12-15

    We demonstrate the manipulation of the Lewis acid strength to selectively fractionate different types of Gd3N metallofullerenes that are present in complex mixtures. Carbon disulfide is used for all Lewis acid studies. CaCl2 exhibits the lowest reactivity but the highest selectivity by precipitating only those gadolinium metallofullerenes with the lowest first oxidation potentials. ZnCl2 selectively complexes Gd3N@C88 during the first 4 h of reaction. Reaction with ZnCl2 for an additional 7 days permits a selective precipitation of Gd3N@C84 as the dominant endohedral isolated. A third fraction is the filtrate, which possesses Gd3N@C86 and Gd3N@C80 as the two dominant metallofullerenes. The order of increasing reactivity and decreasing selectivity (left to right) is as follows: CaCl2 < ZnCl2 < NiCl2 < MgCl2 < MnCl2 < CuCl2 < WCl4 ≪ WCl6 < ZrCl4 < AlCl3 < FeCl3. As a group, CaCl2, ZnCl2, and NiCl2 are the weakest Lewis acids and have the highest selectivity because of their very low precipitation onsets, which are below +0.19 V (i.e., endohedrals with first oxidation potentials below +0.19 V are precipitated). For CaCl2, the precipitation threshold is estimated at a remarkably low value of +0.06 V. Because most endohedrals possess first oxidation potentials significantly higher than +0.06 V, CaCl2 is especially useful in its ability to precipitate only a select group of gadolinium metallofullerenes. The Lewis acids of intermediate reactivity (i.e., precipitation onsets estimated between +0.19 and +0.4 V) are MgCl2, MnCl2, CuCl2, and WCl4. The strongest Lewis acids (WCl6, ZrCl4, AlCl3, and FeCl3) are the least selective and tend to precipitate the entire family of gadolinium metallofullerenes. Tuning the Lewis acid for a specific type of endohedral should be useful in a nonchromatographic purification method. The ability to control which metallofullerenes are permitted to precipitate and which endohedrals would remain in solution is a key outcome of this work.

  17. Metallofullerenes as fuel cell electrocatalysts: a theoretical investigation of adsorbates on C59Pt.

    PubMed

    Gabriel, Margaret A; Genovese, Luigi; Krosnicki, Guillaume; Lemaire, Olivier; Deutsch, Thierry; Franco, Alejandro A

    2010-08-28

    Nano-structured electrode degradation in state-of-the-art polymer electrolyte membrane fuel cells (PEMFCs) is one of the main shortcomings that limit the large-scale development and commercialization of this technology. During normal operating conditions of the fuel cell, the PEMFC lifetime tends to be limited by coarsening of the cathode's Pt-based catalyst and by corrosion of the cathode's carbon black support. Because of their chemical properties, metallofullerenes such as C(59)Pt may be more electrochemically stable than the Pt/C mixture. In this paper we investigate, by theoretical methods, the stability of oxygen reduction reaction (ORR) adsorbates on the metallofullerene C(59)Pt and evaluate its potential as a PEMFC fuel cell catalyst.

  18. A piggyback ride for transition metals: encapsulation of exohedral metallofullerenes in carbon nanotubes.

    PubMed

    Chamberlain, Thomas W; Champness, Neil R; Schröder, Martin; Khlobystov, Andrei N

    2011-01-10

    We have developed a method that enables the efficient insertion of transition-metal atoms and their small clusters into carbon nanotubes. As a model system, Os complexes attached to the exterior of fullerene C60 (exohedral metallofullerenes) were shown to be dragged into the nanotube spontaneously and irreversibly due to strong van der Waals interactions, specific to fullerenes and carbon nanotubes. The size of the metal-containing groups attached to C60 was shown to be critical for successful insertion, as functional groups too bulky to enter the nanotube were stripped off the fullerene during the encapsulation process. Once inside the nanotube, Os atoms catalyse polymerisation and decomposition of fullerene cages, which is related to a much higher catalytic activity of metal atoms situated on the surface of the fullerene cage, as compared to metal atoms in endohedral fullerenes, such as M@C82. Thus, exohedral metallofullerenes show promise for applications in catalysis in carbon “nano” test tubes.

  19. Tuning electronic and magnetic properties of endohedral Co@B80 and exohedral Co-B80 metallofullerenes by positioning Co atom

    NASA Astrophysics Data System (ADS)

    Li, J. L.; Yang, G. W.

    2010-06-01

    We have performed a systematical study of the structural configurations, electronic and magnetic properties of the single Co-doped endohedral Co@B80 and exohedral Co-B80 metallofullerene complexes using spin-polarized density functional calculations. Our calculations revealed that there are four stable configurations of the Co-doped metallofullerenes depending on different positions of the doping Co atoms as follows. In the case of the exohedral Co-B80 metallofullerene complexes, Co atom energetically prefers standing near the centers of pentagon (pentagon-out) and hexagon (hexagon-out) on the surface of B80. In the case of the endohedral Co@B80 metallofullerene complexes, the encapsulated Co atom energetically prefers standing near the centers of pentagon (pentagon-in) and hexagon (hexagon-in) on the inner surface of the hollow cage of B80. Electronically, the energy gaps of the hexagon-near adsorbed metallofullerenes have been greatly modified compared with that of B80. At the same time, the magnetic moments of both of the exohedral Co-B80 metallofullerenes are one third of that of the isolated Co atom. The tunable electronic and magnetic properties of the Co-doped B80 metallofullerenes clearly showed that this new type of metallofullerenes may be a promising candidate for molecular devices, especially single molecular spin electronic devices.

  20. Near-Infrared Photoluminescence Properties of Endohedral Mono- and Dithulium Metallofullerenes.

    PubMed

    Wang, Zhiyong; Izumi, Noriko; Nakanishi, Yusuke; Koyama, Takeshi; Sugai, Toshiki; Tange, Masayoshi; Okazaki, Toshiya; Shinohara, Hisanori

    2016-04-26

    The optical properties of endohedral metallofullerene molecules can be tuned by changing the fullerene size as well as the number of metal atoms inside the fullerene cages. In this work we have synthesized and isolated a series of mono- and dithulium metallofullerenes, including Tm@C82 (isomers I, II, III, IV), Tm@C88 (I-IV), Tm2@C82 (I-III), and (Tm2C2)@C82 (I-III). Near-infrared photoluminescence is observed from the thulium metallofullerenes. By changing the number of Tm ion in the fullerene cage, we have found that one can vary and tune the photoluminescence from 1200 to 1300-2000 nm observed for Tm(2+) (4f(13)) in Tm@C88 and Tm(3+) (4f(12)) in (Tm2C2)@C82, respectively. The photoluminescence intensity depends sensitively on the fullerene cages. (Tm2C2)@C82 (III) exhibits the highest photoluminescence intensity among the three structural isomers because of its large HOMO-LUMO energy gap.

  1. Partial charge transfer in the shortest possible metallofullerene peapod, La@C82 ⊂[11]cycloparaphenylene.

    PubMed

    Iwamoto, Takahiro; Slanina, Zdenek; Mizorogi, Naomi; Guo, Jingdong; Akasaka, Takeshi; Nagase, Shigeru; Takaya, Hikaru; Yasuda, Nobuhiro; Kato, Tatsuhisa; Yamago, Shigeru

    2014-10-27

    [11]Cycloparaphenylene ([11]CPP) selectively encapsulates La@C82 to form the shortest possible metallofullerene-carbon nanotube (CNT) peapod, La@C82 ⊂[11]CPP, in solution and in the solid state. Complexation in solution was affected by the polarity of the solvent and was 16 times stronger in the polar solvent nitrobenzene than in the nonpolar solvent 1,2-dichlorobenzene. Electrochemical analysis revealed that the redox potentials of La@C82 were negatively shifted upon complexation from free La@C82 . Furthermore, the shifts in the redox potentials increased with polarity of the solvent. These results are consistent with formation of a polar complex, (La@C82 )(δ-) ⊂[11]CPP(δ+) , by partial electron transfer from [11]CPP to La@C82 . This is the first observation of such an electronic interaction between a fullerene pea and CPP pod. Theoretical calculations also supported partial charge transfer (0.07) from [11]CPP to La@C82 . The structure of the complex was unambiguously determined by X-ray crystallographic analysis, which showed the La atom inside the C82 near the periphery of the [11]CPP. The dipole moment of La@C82 was projected toward the CPP pea, nearly perpendicular to the CPP axis. The position of the La atom and the direction of the dipole moment in La@C82 ⊂[11]CPP were significantly different from those observed in La@C82 ⊂CNT, thus indicating a difference in orientation of the fullerene peas between fullerene-CPP and fullerene-CNT peapods. These results highlight the importance of pea-pea interactions in determining the orientation of the metallofullerene in metallofullerene-CNT peapods.

  2. Studies of dipalmitoylphosphatidylcholine (DPPC) monolayers embedded with endohedral metallofullerene (Dy@C82).

    PubMed

    Wang, Zhining; Li, Xiaofang; Yang, Shihe

    2009-11-17

    Toxicological effects of carbon nanomaterials have attracted increasing attention. In this work, we studied the interaction between Dy@C(82) and dipalmitoylphosphatidylcholine (DPPC) in a monolayer at the N(2)/Tris buffer interface by thermodynamic analysis of surface pressure-area (pi-A) and surface potential-area (DeltaV-A) isotherms. Dy@C(82) was found to impact considerably more on the physical properties of the monolayers than C(60) because of its elliptical structure and distinctive dipole. The addition of Dy@C(82) essentially closed down the liquid expanded-liquid condensed (LE-LC) phase coexistence region of the mixed monolayers. Furthermore, Dy@C(82) reduced elasticity of the monolayers, as indicated by the decreasing elastic modulus (C(s)(-1)) with increasing molar ratio of Dy@C(82) (X(Dy@C82)). Brewster angle microscopy (BAM) and atomic force microscopy (AFM) revealed that the dispersion of Dy@C(82) depend on the state of the mixed films. Dy@C(82) formed flocs from aggregation of Dy@C(82) towers in the LE and LE-LC coexistence regions, accompanied by gradual falling down of Dy@C(82) from the towers and permeation of the falling metallofullerenes into the LE phase during their compression-induced reorientation process. In the LC and solid phases, the Dy@C(82) flocs were dispersed into isolated towers, accompanied by the partial squeezing out of the embedded metallofullerenes to above the DPPC monolayer. The continuous falling down of Dy@C(82) from the towers resulted in their height decrease but diameter enlargement. When the surface pressure was increased to the kink value (53 mN/m), Dy@C(82) was almost completely extruded from the DPPC monolayers. These findings are believed to be important for understanding the impact of fullerenes, metallofullerenes, and nanomaterials in general on biological membranes.

  3. An ab initio investigation on the endohedral metallofullerene Gd3N-C80

    NASA Astrophysics Data System (ADS)

    Qian, M. C.; Khanna, S. N.

    2007-05-01

    First-principles electronic structure studies on the ground state geometry and electronic and magnetic properties of bare and hydrogen coated metallofullerene Gd3N-C80 have been carried out within a density functional formalism. The correlation effects are incorporated either through a generalized gradient corrected functional or through an on-site Coulomb interaction (LDA+U). It is shown that the bare Gd3N-C80 possess a ferromagnetic ground state with a large spin moment of 21μB that is highly stable against spin fluctuations. The simulated Raman spectrum shows that the low-energy peaks are contributed by the floppy movement of N atom. As to the effect of addition of hydrogens, it is shown that the most favorable site for the hydrogen adsorption is an on-top site where the H atom is located above a five-member carbon ring with a binding energy of 1.92eV, while the least stable site corresponds to an on-top absorption above a six-member ring. A study of the energetics upon multiple adsorption of H shows that the binding energy of the H to metallofullerene drops after 11 H atoms. This shows that it should be possible to attach multiple ligands offering the potential that the Gd3N-C80 can be functionalized with ligands or assembled in cluster assemblies.

  4. Metallofullerene-Nanoplatform-Delivered Interstitial Brachytherapy Improved Survival in a Murine Model of Glioblastoma Multiforme

    PubMed Central

    Wilson, John D.; Broaddus, William C.; Dorn, Harry C.; Fatouros, Panos P.; Chalfant, Charles E.; Shultz, Michael D.

    2012-01-01

    Fullerenes are used across scientific disciplines because of their diverse properties gained by altering encapsulated or surface bound components. In this study, the recently developed theranostic agent based on a radiolabeled functionalized metallofullerene (177Lu-DOTA-f-Gd3N@C80) was synthesized with high radiochemical yield and purity. The efficacy of this agent was demonstrated in two orthotopic xenograft brain tumor models of glioblastoma multiforme (GBM). A dose-dependent improvement in survival was also shown. The in vivo stability of the agent was verified through dual label measurements of biological elimination from the tumor. Overall, these results provide evidence that nanomaterial platforms can be used to deliver effective interstitial brachytherapy. PMID:22881865

  5. Development of Electron Cyclotron Resonance Ion Source for Synthesis of Endohedral Metallofullerenes

    SciTech Connect

    Tanaka, K.; Muramatsu, M.; Uchida, T.; Hanajiri, T.; Yoshida, Y.; Biri, S.; Kitagawa, A.; Kato, Y.

    2008-11-03

    A new electron cyclotron resonance ion source (ECRIS) has been constructed for synthesis of endohedral metallofullerenes. The main purpose of the ion source is to produce new biological and medical materials. The design is based on ECRIS for production of multicharged ion beams with a traditional minimum-B magnetic field. An 8-10 GHz traveling wave tube (TWT) amplifier and a 2.45 GHz magnetron have been applied as microwave sources. Fullerene and metal vapor are introduced with a filament heating micro-oven and an induction heating oven, respectively. In preliminary ion-extraction test, Ar{sup +} is 54 {mu}A. Many broken fullerenes such as C{sub 58} and C{sub 56} are observed in fullerene ion beams.

  6. Molecular Location Sensing Approach by Anisotropic Magnetism of an Endohedral Metallofullerene.

    PubMed

    Takano, Yuta; Tashita, Ryo; Suzuki, Mitsuaki; Nagase, Shigeru; Imahori, Hiroshi; Akasaka, Takeshi

    2016-06-29

    Location recognition at the molecular scale provides valuable information about the nature of functional molecular materials. This study presents a novel location sensing approach based on an endohedral metallofullerene, Ce@C82, using its anisotropic magnetic properties, which lead to temperature-dependent paramagnetic shifts in (1)H NMR spectra. Five site-isomers of Ce@C82CH2-3,5-C6H3Me2 were synthesized to demonstrate the spatial sensing ability of Ce@C82. Single-crystal structures, absorption spectra, and density functional theory calculations were used to select the plausible addition positions in the radical coupling reaction, which preferentially happens on the carbon atoms with high electron density of the singly occupied molecular orbital (SOMO) and positive charge. Temperature-dependent NMR measurements demonstrated unique paramagnetic shifts of the (1)H peaks, which were derived from the anisotropic magnetism of the f-electron in the Ce atom of the isomers. It was found that the magnetic anisotropy axes can be easily predicted by theoretical calculations using the Gaussian 09 package. Further analysis revealed that the temperature-dependent trend in the shifts is clearly predictable from the distance and relative position of the proton from the Ce atom. Hence, the Ce-encapsulated metallofullerene Ce@C82 can provide spatial location information about nearby atoms through the temperature-dependent paramagnetic shifts of its NMR signals. It can act as a molecular probe for location sensing by utilizing the anisotropic magnetism of the encapsulated Ce atom. The potentially low toxicity and stability of the endohedral fullerene would make Ce@C82 suitable for applications in biology and material science.

  7. Visible and near-IR spectroscopy of endohedral Gd@C82( C 2 v ) and Ho@C82( C 2 v ) metallofullerenes and their monoanions

    NASA Astrophysics Data System (ADS)

    Kareev, I. E.; Nekrasov, V. M.; Dutlov, A. E.; Martynenko, V. M.; Bubnov, V. P.; Laukhina, E.; Veciana, J.; Rovira, C.

    2017-03-01

    Solutions of endohedral Gd@C82( C 2 v ) and Ho@C82( C 2 v ) metallofullerenes are studied by means of visible and near-IR spectroscopy upon their conversion from neutral to the anionic form via a redox reaction with the electron donor potassium perchlorotriphenylmethide K(18-crown-6)[C(C6Cl5)3]. The concentrations of the studied solutions of endohedral Gd@C82( C 2 v ) and Ho@C82( C 2 v ) metallofullerenes in o-dichlorobenzene were determined from the spectroscopic data, and their molar extinction coefficients are calculated.

  8. Electron transport in endohedral metallofullerene Ce@C{sub 82} single-molecule transistors

    SciTech Connect

    Okamura, Naoya; Yoshida, Kenji; Sakata, Shuichi; Hirakawa, Kazuhiko

    2015-01-26

    We have investigated the electron transport in endohedral metallofullerene Ce@C{sub 82} single-molecule transistors (SMTs) together with that in reference C{sub 84} SMTs. The vibrational modes (bending and stretching) of the encapsulated single Ce atom in the C{sub 82} cage appear in Coulomb stability diagrams for the single-electron tunneling through Ce@C{sub 82} molecules, demonstrating the single-atom sensitivity of the transport measurements. When a bias voltage larger than 100 mV is applied across the source/drain electrodes, large hysteretic behavior is observed in the current-voltage (I-V) characteristics. At the same time, the pattern in the Coulomb stability diagram is changed. No such hysteretic behavior is observed in the I-V curves of hollow-cage C{sub 84} SMTs, even when the bias voltage exceeds 500 mV. This hysteretic change in the I-V characteristics is induced by a nanomechanical change in the configuration of the Ce@C{sub 82} molecule in the nanogap electrode due to the electric dipole that exists in Ce@C{sub 82}.

  9. Exploration in metallic nitride fullerenes and oxometallic fullerenes: A new class of metallofullerenes

    NASA Astrophysics Data System (ADS)

    Mackey, Mary Alice

    2011-07-01

    Research groups around the world have taken an interest in the synthesis, purification, characterization, and functionalization of Metallic Nitride Fullerenes (MNFs) since their discovery in 1999. This dissertation details the discovery of another new class of molecules---Oxometallic Fullerenes (OMFs). There are many groups worldwide doing research on MNFs, and there is a large database of published MNF research, but we have had a unique opportunity to fill a research void on OMFs as at present no one else is doing research on these molecules; herein we take molecules that we discover and perform seminal research relating to them. MNF research is closely tied to this project; MNFs are a stepping stone because of their greater abundance and similar reactivity. Building off of previously developed techniques, we are able to create new methods for the separation and isolation of MNFs and OMFs. We studied the reactivity differences of various MNFs and OMFs in order to utilize Lewis acid chemistry as a tool for the enrichment and purification of both MNFs and OMFs, eventually resulting in a detailed separations technique. We have also begun studies to functionalize the carbon cage of endohedral metallofullerenes---this research includes using Lewis acids and various aromatic solvents via Friedel-Crafts reactions.

  10. A Versatile and Clearable Nanocarbon Theranostic Based on Carbon Dots and Gadolinium Metallofullerene Nanocrystals.

    PubMed

    Guan, Mirong; Li, Jie; Jia, Qingyan; Ge, Jiechao; Chen, Daiqin; Zhou, Yue; Wang, Pengfei; Zou, Toujun; Zhen, Mingming; Wang, Chunru; Shu, Chunying

    2016-09-01

    Nanocarbons such as carbon nanotubes, graphene derivatives, and carbon nanohorns have illustrated their potential uses as cancer theranostics owing to their intrinsic fluorescence or NIR absorbance as well as superior cargo loading capacity. However, some problems still need to be addressed, such as the fates and long-term toxicology of different nanocarbons in vivo and the improvement of their performance in various biomedical imaging-guided cancer therapy systems. Herein, a versatile and clearable nanocarbon theranostic based on carbon dots (CDs) and gadolinium metallofullerene nanocrystals (GFNCs) is first developed, in which GFNCs enhance the tumor accumulation of CDs, and CDs enhance the relaxivity of GFNCs, leading to an efficient multimodal imaging-guided photodynamic therapy in vivo without obvious long-term toxicity. Furthermore, biochemical analysis reveals that the novel nanotheranostic can harmlessly eliminate from the body in a reasonable period of time after exerting diagnostic and therapeutic function. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Photoionization of Au+ ions and developments in the synthesis of the metallofullerene Au@C60

    NASA Astrophysics Data System (ADS)

    Bogolub, Kyren; Macaluso, David; Mueller, Allison; Johnson, Andrea; Müller, Alfred; Schippers, Stefan; Hellhund, Jonas; Borovik, Alexander; Anders, Andre; Aguilar, Alex; Kilcoyne, A. L. David

    2014-05-01

    Single photoionization of Au+ ions was investigated via the merged-beams technique at AMO Beamline 10.0.1.2 of the Advanced Light Source at Lawrence Berkeley National Laboratory. The relative single photoionization yield was measured as a function of photon energy in the 45 eV to 120 eV energy range. These measurements were made in preparation for future photoionization studies of the endohedral metallofullerene Au@C60, the production of which was also investigated. In proof-of-principle measurements a mass-resolved beam of Au@C60+was produced with a primary ion beam current in the single picoamp range without optimization of the ion source or synthesis parameters. Plans are presented for improved metallofullere production yield to be used in photoionization measurements of the endohedral fullerene ions in conjunction with the continuing study of pure Au. We would like to acknowledge the generous sharing of equipment vital to this work by Andre Anders, the Plasma Applications group leader at the Advanced Light Source, LBNL.

  12. Metabolizer in vivo of fullerenes and metallofullerenes by positron emission tomography

    NASA Astrophysics Data System (ADS)

    Li, Juan; Yang, Wenjiang; Cui, Rongli; Wang, Dongliang; Chang, Yanan; Gu, Weihong; Yin, Wenyan; Bai, Xue; Chen, Kui; Xia, Lin; Geng, Huan; Xing, Gengmei

    2016-04-01

    Fullerenes (C60) and metallofullerenes (Gd@C82) have similar chemical structure, but the bio-effects of both fullerene-based materials are distinct in vivo. Tracking organic carbon-based materials such as C60 and Gd@C82 is difficult in vivo due to the high content of carbon element in the living tissues themselves. In this study, the biodistribution and metabolism of fullerenes (C60 and Gd@C82) radiolabeled with 64Cu were observed by positron emission tomography (PET). 64Cu-C60 and 64Cu-Gd@C82 were prepared using 1, 4, 7, 10-tetrakis (carbamoylmethyl)-1, 4, 7, 10-tetra-azacyclodo-decanes grafted on carbon cages as a chelator for 64Cu, and were obtained rapidly with high radiochemical yield (≥90%). The new radio-conjugates were evaluated in vivo in the normal mouse model and tissue distribution by small animal PET/CT imaging and histology was carried out. The PET imaging, the biodistribution and the excretion of C60 and Gd@C82 indicated that C60 samples have higher blood retention and lower renal clearance than the Gd@C82 samples in vivo and suggested that the differences in metabolism and distribution in vivo were caused by the structural differences of the groups on the fullerene cages though there is chemical similarity between C60 and Gd@C82.

  13. Use of trimetasphere metallofullerene MRI contrast agent for the non-invasive longitudinal tracking of stem cells in the lung

    PubMed Central

    Murphy, Sean V.; Hale, Austin; Reid, Tanya; Olson, John; Kidiyoor, Amritha; Tan, Josh; Zhou, Zhiguo; Jackson, John; Atala, Anthony

    2016-01-01

    Magnetic Resonance Imaging (MRI) is a commonly used, non-invasive imaging technique that provides visualization of soft tissues with high spatial resolution. In both a research and clinical setting, the major challenge has been identifying a non-invasive and safe method for longitudinal tracking of delivered cells in vivo. The labeling and tracking of contrast agent labeled cells using MRI has the potential to fulfill this need. Contrast agents are often used to enhance the image contrast between the tissue of interest and surrounding tissues with MRI. The most commonly used MRI contrast agents contain Gd(III) ions. However, Gd(III) ions are highly toxic in their ionic form, as they tend to accumulate in the liver, spleen, kidney and bones and block calcium channels. Endohedral metallofullerenes such as trimetallic nitride endohedral metallofullerenes (Trimetasphere®) are one unique class of fullerene molecules where a Gd3N cluster is encapsulated inside a C80 carbon cage referred to as Gd3N@C80. These endohedral metallofullerenes have several advantages over small chelated Gd(III) complexes such as increased stability of the Gd(III) ion, minimal toxic effects, high solubility in water and high proton relativity. In this study, we describe the evaluation of gadolinium-based Trimetasphere® positive contrast agent for the in vitro labeling and in vivo tracking of human amniotic fluid-derived stem cells within lung tissue. In addition, we conducted a ‘proof-of-concept’ experiment demonstrating that this methodology can be used to track the homing of stem cells to injured lung tissue and provide longitudinal analysis of cell localization over an extended time course. PMID:26546729

  14. Use of trimetasphere metallofullerene MRI contrast agent for the non-invasive longitudinal tracking of stem cells in the lung.

    PubMed

    Murphy, Sean V; Hale, Austin; Reid, Tanya; Olson, John; Kidiyoor, Amritha; Tan, Josh; Zhou, Zhiguo; Jackson, John; Atala, Anthony

    2016-04-15

    Magnetic Resonance Imaging (MRI) is a commonly used, non-invasive imaging technique that provides visualization of soft tissues with high spatial resolution. In both a research and clinical setting, the major challenge has been identifying a non-invasive and safe method for longitudinal tracking of delivered cells in vivo. The labeling and tracking of contrast agent labeled cells using MRI has the potential to fulfill this need. Contrast agents are often used to enhance the image contrast between the tissue of interest and surrounding tissues with MRI. The most commonly used MRI contrast agents contain Gd(III) ions. However, Gd(III) ions are highly toxic in their ionic form, as they tend to accumulate in the liver, spleen, kidney and bones and block calcium channels. Endohedral metallofullerenes such as trimetallic nitride endohedral metallofullerenes (Trimetasphere®) are one unique class of fullerene molecules where a Gd3N cluster is encapsulated inside a C80 carbon cage referred to as Gd3N@C80. These endohedral metallofullerenes have several advantages over small chelated Gd(III) complexes such as increased stability of the Gd(III) ion, minimal toxic effects, high solubility in water and high proton relativity. In this study, we describe the evaluation of gadolinium-based Trimetasphere® positive contrast agent for the ​in vitro labeling and in vivo tracking of human amniotic fluid-derived stem cells within lung tissue. In addition, we conducted a 'proof-of-concept' experiment demonstrating that this methodology can be used to track the homing of stem cells to injured lung tissue and provide longitudinal analysis of cell localization over an extended time course. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. The metallofullerene field-induced single-ion magnet HoSc2 N@C80.

    PubMed

    Dreiser, Jan; Westerström, Rasmus; Zhang, Yang; Popov, Alexey A; Dunsch, Lothar; Krämer, Karl; Liu, Shi-Xia; Decurtins, Silvio; Greber, Thomas

    2014-10-13

    The low-temperature magnetic properties of the endohedral metallofullerene HoSc2 N@C80 have been studied by superconducting quantum interference device (SQUID) magnetometry. Alternating current (ac) susceptibility measurements reveal that this molecule exhibits slow relaxation of magnetization in a small applied field with timescales in the order of milliseconds. The equilibrium magnetic properties of HoSc2 N@C80 indicate strong magnetic anisotropy. The large differences in magnetization relaxation times between the present compound and the previously investigated DySc2 N@C80 are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. STM/STS investigations of fullerene C(60), endohedral metallofullerenes M C(82) and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Lin, Nian

    Since their discovery, fullerenes and their derivatives have received great attentions because they opened many new fields in science and technology. Among them, endohedral fullerenes, fullerenes encapsulating one or more atoms in their hollow carbon cases, have been predicted to have novel properties which are unexpected for empty fullerenes. However, the difficulty in producing pure samples of endohedral fullerenes in large quantities have hindered their experimental exploration. The motivation of this research is to understand their properties. In this research, endohedral monometallofullerenes M@Csb{82} (M = Nd, Dy) have been investigated by in-situ ultra high vacuum scanning tunneling microscopy and tunneling spectroscopy. As a comparison, the well-understood fullerene Csb{60} has been studied first by the same technique. On the basal plane of cleaved highly oriented pyrolytic graphite (HOPG) (0001) surface, arriving Csb{60} molecules assemble and grow into highly ordered, extended overlayers in hexagonal-close-packing. Starting from the second layer, the growth mode of Csb{60} transforms from 2-dimensional dendrite islanding to 3-dimensional island formation upon the variation of growth rate and substrate temperature. A band gap of 1.5 ± 0.2 eV is observed in the tunneling spectroscopy of the Csb{60} films. On the contrary, endohedral metallofullerenes do not form ordered structures on HOPG surface under the same conditions of growing Csb{60} films, instead, they gather into clumped clusters. These molecules may induce a symmetric distributed (sqrt{3}×sqrt{3})R30sp° superstructure of the HOPG substrate around them. The superstructure can be realized theoretically by a computer simulation. The HOMO-LUMO gap of a single molecule is measured to be 0.6 ± 0.2 eV by tunneling spectroscopy, consistent with the UV-VIS-Near IR absorption spectrum of M@Csb{82}. On the top of Csb{60} films, Nd@Csb{82} molecules form close-packed 2-D structures of dimers, trimers

  17. Metallofullerene and fullerene formation from condensing carbon gas under conditions of stellar outflows and implication to stardust.

    PubMed

    Dunk, Paul W; Adjizian, Jean-Joseph; Kaiser, Nathan K; Quinn, John P; Blakney, Gregory T; Ewels, Christopher P; Marshall, Alan G; Kroto, Harold W

    2013-11-05

    Carbonaceous presolar grains of supernovae origin have long been isolated and are determined to be the carrier of anomalous (22)Ne in ancient meteorites. That exotic (22)Ne is, in fact, the decay isotope of relatively short-lived (22)Na formed by explosive nucleosynthesis, and therefore, a selective and rapid Na physical trapping mechanism must take place during carbon condensation in supernova ejecta. Elucidation of the processes that trap Na and produce large carbon molecules should yield insight into carbon stardust enrichment and formation. Herein, we demonstrate that Na effectively nucleates formation of Na@C60 and other metallofullerenes during carbon condensation under highly energetic conditions in oxygen- and hydrogen-rich environments. Thus, fundamental carbon chemistry that leads to trapping of Na is revealed, and should be directly applicable to gas-phase chemistry involving stellar environments, such as supernova ejecta. The results indicate that, in addition to empty fullerenes, metallofullerenes should be constituents of stellar/circumstellar and interstellar space. In addition, gas-phase reactions of fullerenes with polycyclic aromatic hydrocarbons are investigated to probe "build-up" and formation of carbon stardust, and provide insight into fullerene astrochemistry.

  18. Metallofullerene and fullerene formation from condensing carbon gas under conditions of stellar outflows and implication to stardust

    PubMed Central

    Dunk, Paul W.; Adjizian, Jean-Joseph; Kaiser, Nathan K.; Quinn, John P.; Blakney, Gregory T.; Ewels, Christopher P.; Marshall, Alan G.; Kroto, Harold W.

    2013-01-01

    Carbonaceous presolar grains of supernovae origin have long been isolated and are determined to be the carrier of anomalous 22Ne in ancient meteorites. That exotic 22Ne is, in fact, the decay isotope of relatively short-lived 22Na formed by explosive nucleosynthesis, and therefore, a selective and rapid Na physical trapping mechanism must take place during carbon condensation in supernova ejecta. Elucidation of the processes that trap Na and produce large carbon molecules should yield insight into carbon stardust enrichment and formation. Herein, we demonstrate that Na effectively nucleates formation of Na@C60 and other metallofullerenes during carbon condensation under highly energetic conditions in oxygen- and hydrogen-rich environments. Thus, fundamental carbon chemistry that leads to trapping of Na is revealed, and should be directly applicable to gas-phase chemistry involving stellar environments, such as supernova ejecta. The results indicate that, in addition to empty fullerenes, metallofullerenes should be constituents of stellar/circumstellar and interstellar space. In addition, gas-phase reactions of fullerenes with polycyclic aromatic hydrocarbons are investigated to probe “build-up” and formation of carbon stardust, and provide insight into fullerene astrochemistry. PMID:24145444

  19. Trimetallic nitride template endohedral metallofullerenes: discovery, structural characterization, reactivity, and applications.

    PubMed

    Zhang, Jianyuan; Stevenson, Steven; Dorn, Harry C

    2013-07-16

    Shortly after the discovery of the carbon fullerene allotrope, C₆₀, researchers recognized that the hollow spheroidal shape could accommodate metal atoms, or clusters, which quickly led to the discovery of endohedral metallofullerenes (EMFs). In the past 2 decades, the unique features of EMFs have attracted broad interest in many fields, including inorganic chemistry, organic chemistry, materials chemistry, and biomedical chemistry. Some EMFs produce new metallic clusters that do not exist outside of a fullerene cage, and some other EMFs can boost the efficiency of magnetic resonance (MR) imaging 10-50-fold, in comparison with commercial contrast agents. In 1999, the Dorn laboratory discovered the trimetallic nitride template (TNT) EMFs, which consist of a trimetallic nitride cluster and a host fullerene cage. The TNT-EMFs (A₃N@C2n, n = 34-55, A = Sc, Y, or lanthanides) are typically formed in relatively high yields (sometimes only exceeded by empty-cage C₆₀ and C₇₀, but yields may decrease with increasing TNT cluster size), and exhibit high chemical and thermal stability. In this Account, we give an overview of TNT-EMF research, starting with the discovery of these structures and then describing their synthesis and applications. First, we describe our serendipitous discovery of the first member of this class, Sc₃N@Ih-C₈₀. Second, we discuss the methodology for the synthesis of several TNT-EMFs. These results emphasize the importance of chemically adjusting plasma temperature, energy, and reactivity (CAPTEAR) to optimize the type and yield of TNT-EMFs produced. Third, we review the approaches that are used to separate and purify pristine TNT-EMF molecules from their corresponding product mixtures. Although we used high-performance liquid chromatography (HPLC) to separate TNT-EMFs in early studies, we have more recently achieved facile separation based on the reduced chemical reactivity of the TNT-EMFs. These improved production yields and

  20. Molecular structure and chemical property of a divalent metallofullerene Yb@C2(13)-C84.

    PubMed

    Zhang, Wenjun; Suzuki, Mitsuaki; Xie, Yunpeng; Bao, Lipiao; Cai, Wenting; Slanina, Zdenek; Nagase, Shigeru; Xu, Ming; Akasaka, Takeshi; Lu, Xing

    2013-08-28

    Endohedral metallofullerenes (EMFs) encapsulating divalent metal ions have received limited attention because of their low production yields. Here, we report the results of structural determination and chemical functionalization of a typical divalent metallofullerene, Yb@C84(II). Single-crystal X-ray crystallographic studies of Yb@C84/Ni(II)(OEP) cocrystals (OEP is the dianion of octaethylporphyrin) unambiguously established the chiral C2(13)-C84 cage structure and revealed multiple sites for Yb(2+), indicating a moving metal ion inside the cage. The chemical property of Yb@C2(13)-C84 was probed with the electrophillic adamantylidene carbene (1). Three monoadduct isomers were isolated and characterized. Crystallographic results of the major isomer (2b) revealed that, although the cycloaddition breaks a [5,6]-bond on the cage, Yb(2+) is localized under a hexagonal ring distant from the sites of addition. Thus, it is proved that the dynamic motion of the divalent metal ion in Yb@C84 has been effectively halted by exohedral functionalization. Spectroscopic results show that the electronic property of Yb@C2(13)-C84 is pertained in the derivatives, although the addend exerts a mild reduction effect on the electrochemical behavior of the EMF. Computational works demonstrated that addition of 1 to Yb@C2(13)-C84 is mainly driven by releasing the local strains of cage carbons rather than charge recombination, which is always prominent to the affinity of typical trivalent EMFs such as M@C2v(9)-C82 (M = Sc, Y, La, Ce, Gd) toward 1. Accordingly, it is speculated that the chemical behaviors of divalent EMFs more likely resemble those of empty fullerenes because both are closed-shell compounds, but they differ from those of trivalent EMFs, which have open-shell electronic configurations instead.

  1. Unprecedented chemical reactivity of a paramagnetic endohedral metallofullerene La@C(s)-C82 that leads hydrogen addition in the 1,3-dipolar cycloaddition reaction.

    PubMed

    Takano, Yuta; Slanina, Zdenek; Mateos, Jaime; Tsuchiya, Takayoshi; Kurihara, Hiroki; Uhlik, Filip; Herranz, María Ángeles; Martín, Nazario; Nagase, Shigeru; Akasaka, Takeshi

    2014-12-17

    Synthesizing unprecedented diamagnetic adducts of an endohedral metallofullerene was achieved by using 1,3-dipolar cycloaddition reaction of paramagnetic La@C(s)-C82 with a simultaneous hydrogen addition. The selective formation of two main products, La@C(s)-C82HCMe2NMeCHPh (2a and 2b), was first detected by HPLC analysis and MALDI-TOF mass spectrometry. 2a and 2b-O, which was readily formed by the oxidation of 2b, were isolated by multistep HPLC separation and were fully characterized by spectroscopic methods, including 1D and 2D-NMR, UV-vis-NIR measurements and electrochemistry. The hydrogen atom was found to be connected to the fullerene cage directly in the case of 2a, and the redox behavior indicated that the C-H bond can still be readily oxidized. The reaction mechanism and the molecular structures of 2a and 2b were reasonably proposed by the interplay between experimental observations and DFT calculations. The feasible order of the reaction process would involve a 1,3-dipolar cycloaddition followed by the hydrogen addition through a radical pathway. It is concluded that the characteristic electronic properties and molecular structure of La@C(s)-C82 resulted in a site-selective reaction, which afforded a unique chemical derivative of an endohedral metallofullerene in high yields. Derivative 2a constitutes the first endohedral metallofullerene where the direct linking of a hydrogen atom has been structurally proven.

  2. Low-toxic and safe nanomaterials by surface-chemical design, carbon nanotubes, fullerenes, metallofullerenes, and graphenes

    NASA Astrophysics Data System (ADS)

    YanEqual Contribution, Liang; Zhao, Feng; Li, Shoujian; Hu, Zhongbo; Zhao, Yuliang

    2011-02-01

    The toxicity grade for a bulk material can be approximately determined by three factors (chemical composition, dose, and exposure route). However, for a nanomaterial it depends on more than ten factors. Interestingly, some nano-factors (like huge surface adsorbability, small size, etc.) that endow nanomaterials with new biomedical functions are also potential causes leading to toxicity or damage to the living organism. Is it possible to create safe nanomaterials if such a number of complicated factors need to be regulated? We herein try to find answers to this important question. We first discuss chemical processes that are applicable for nanosurface modifications, in order to improve biocompatibility, regulate ADME, and reduce the toxicity of carbon nanomaterials (carbon nanotubes, fullerenes, metallofullerenes, and graphenes). Then the biological/toxicological effects of surface-modified and unmodified carbon nanomaterials are comparatively discussed from two aspects: the lowered toxic responses or the enhanced biomedical functions. We summarize the eight biggest challenges in creating low-toxicity and safer nanomaterials and some significant topics of future research needs: to find out safer nanofactors; to establish controllable surface modifications and simpler chemistries for low-toxic nanomaterials; to explore the nanotoxicity mechanisms; to justify the validity of current toxicological theories in nanotoxicology; to create standardized nanomaterials for toxicity tests; to build theoretical models for cellular and molecular interactions of nanoparticles; and to establish systematical knowledge frameworks for nanotoxicology.

  3. A complete guide on the influence of metal clusters in the Diels-Alder regioselectivity of I(h)-C80 endohedral metallofullerenes.

    PubMed

    Garcia-Borràs, Marc; Osuna, Sílvia; Luis, Josep M; Swart, Marcel; Solà, Miquel

    2013-10-25

    The chemical functionalization of endohedral metallofullerenes (EMFs) has aroused considerable interest due to the possibility of synthesizing new species with potential applications in materials science and medicine. Experimental and theoretical studies on the reactivity of endohedral metallofullerenes are scarce. To improve our understanding of the endohedral metallofullerene reactivity, we have systematically studied with DFT methods the Diels-Alder cycloaddition between s-cis-1,3-butadiene and practically all X@I(h)-C80 EMFs synthesized to date: X=Sc3N, Lu3N, Y3N, La2, Y3, Sc3C2, Sc4C2, Sc3CH, Sc3NC, Sc4O2 and Sc4O3. We have studied both the thermodynamic and kinetic regioselectivity, taking into account the free rotation of the metallic cluster inside the fullerene. This systematic study has been made possible through the use of the frozen cage model (FCM), a computationally cheap approach to accurately predicting the exohedral regioselectivity of cycloaddition reactions in EMFs. Our results show that the EMFs are less reactive than the hollow I(h)-C80 cage. Except for the Y3 cluster, the additions occur predominantly at the [5,6] bond. In many cases, however, a mixture of the two possible regioisomers is predicted. In general, [6,6] addition is favored in EMFs that have a larger charge transfer from the metal cluster to the cage or a voluminous metal cluster inside. The present guide represents the first complete and exhaustive investigation of the reactivity of I(h)-C80-based EMFs.

  4. Self-assembly of endohedral metallofullerenes: a decisive role of cooling gas and metal-carbon bonding

    NASA Astrophysics Data System (ADS)

    Deng, Qingming; Heine, Thomas; Irle, Stephan; Popov, Alexey A.

    2016-02-01

    The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc-C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-Td and Ti@C30-C2v(3).The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i

  5. Bonding between strongly repulsive metal atoms: an oxymoron made real in a confined space of endohedral metallofullerenes.

    PubMed

    Popov, Alexey A; Avdoshenko, Stas M; Pendás, Angel Martín; Dunsch, Lothar

    2012-08-21

    Endohedral metallofullerenes (EMFs) are able to encapsulate up to four metal atoms. In EMFs, metal atoms are positively charged because of the electron transfer from the endohedral metal atoms to the carbon cage. It results in the strong Coulomb repulsion between the positively charged ions trapped in the confined inner space of the fullerene. At the same time, in many EMFs, such as Lu(2)@C(76), Y(2)@C(79)N, M(2)@C(82) (M = Sc, Y, Lu, etc.), Y(3)@C(80), or Sc(4)O(2)@C(80), metals do not adopt their highest oxidation states, thus yielding a possibility of the covalent metal-metal bonding. In some other EMFs (e.g., La(2)@C(80)), metal-metal bonding evolves as the result of the electrochemical or chemical reduction, which leads to the population of the metal-based LUMO with pronounced metal-metal bonding character. This article highlights different aspects of the metal-metal bonding in EMFs. It is concluded that the valence state of the metal atoms in dimetallofullerenes is not dependent on their third ionization potential, but is determined by their ns(2)(n- 1)d(1)→ns(1)(n- 1)d(2) excitation energies. Peculiarities of the metal-metal bonding in EMFs are described in terms of molecular orbital analysis as well as topological approaches such as Quantum Theory of Atoms in Molecules and Electron Localization Function. Interplay of Coulomb repulsion and covalent bonding is analyzed in the framework of the Interacting Quantum Atom approach.

  6. Self-assembly of endohedral metallofullerenes: a decisive role of cooling gas and metal-carbon bonding.

    PubMed

    Deng, Qingming; Heine, Thomas; Irle, Stephan; Popov, Alexey A

    2016-02-14

    The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc-C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-Td and Ti@C30-C2v(3).

  7. Structures and nonlinear optical properties of the endohedral metallofullerene-superhalogen compounds Li@C60-BX4 (X = F, Cl, Br).

    PubMed

    Wang, Shu-Jian; Li, Ying; Wang, Yin-Feng; Wu, Di; Li, Zhi-Ru

    2013-08-21

    It has recently been demonstrated that superatoms, which can exhibit behaviors reminiscent of atoms in the periodic table, might have synthetic utility, and represent potential building blocks for the assembly of novel, nanostructured materials [Science 2004, 304, 84-87; Science 2005, 307, 231-235; J. Phys. Chem. C 2009, 113, 2664]. In this work, a new type of endohedral metallofullerene-superhalogen compound, Li@C60-BX4 (X = F, Cl, Br), is proposed and characterized using density functional theory. The electron transfer from Li@C60 to BX4 contributes greatly to the Li@C60-BX4 compound formation. Such compounds exhibit considerable stabilities with large binding energies and ionization potentials, as well as large HOMO-LUMO gaps. The investigation of the nonlinear optical (NLO) properties of Li@C60-BX4 reveals a strong dependence of the static first hyperpolarizability, β0, on the atomic number of the involved halogen atom X. This means that one can enhance the first hyperpolarizabilities of the endohedral metallofullerene by introducing superhalogens. The present investigation may promote the development of novel nanomaterials with unusual properties (i.e. NLO properties), and enrich the knowledge of chemical bonds (for example, long-range interactions between trapped atoms in a C60 cage and the outside superatom motif).

  8. Metallofullerene-based Nanoplatform for Brain Tumor Brachytherapy and Longitudinal Imaging in a Murine Orthotopic Xenograft Model

    PubMed Central

    Shultz, Michael D.; Wilson, John D.; Fuller, Christine E.; Zhang, Jianyuan; Dorn, Harry C.

    2011-01-01

    Purpose: To demonstrate in an orthotopic xenograft brain tumor model that a functionalized metallofullerene (f-Gd3N@C80) can enable longitudinal tumor imaging and, when radiolabeled with lutetium 177 (177Lu) and tetraazacyclododecane tetraacetic acid (DOTA) (177Lu-DOTA-f-Gd3N@C80), provide an anchor to deliver effective brachytherapy. Materials and Methods: All experiments involving the use of mice were carried out in accordance with protocols approved by the institutional animal care and use committee. Human glioblastoma U87MG cells were implanted by using stereotactic procedures into the brains of 37 female athymic nude-Foxn1nu mice and allowed to develop into a tumor for 8 days. T1- and T2-weighted magnetic resonance (MR) imaging was performed in five mice. Biodistribution studies were performed in 12 mice at four time points over 7 days to evaluate gadolinium content. Survival studies involved 20 mice that received infusion of a nanoplatform by means of convection-enhanced delivery (CED) 8 days after tumor implantation. Mice in survival studies were divided into two groups: one comprised untreated mice that received f-Gd3N@C80 alone and the other comprised mice treated with brachytherapy that received 1.11 MBq of 177Lu-DOTA-f-Gd3N@C80. Survival data were evaluated by using Kaplan-Meier statistical methods. Results: MR imaging showed extended tumor retention (25.6% ± 1.2 of the infused dose at 52 days, confirmed with biodistribution studies) of the f-Gd3N@C80 nanoplatform, which enabled longitudinal imaging. Successful coupling of 177Lu to the f-Gd3N@C80 surface was achieved by using a bifunctional macrocyclic chelator. The extended tumor retention allowed for effective brachytherapy, as indicated by extended survival time (>2.5 times that of the untreated group) and histologic signs of radiation-induced tumor damage. Conclusion: The authors have developed a multimodal nanoplatform and have demonstrated longitudinal tumor imaging, prolonged intratumoral probe

  9. Encapsulation of a radiolabeled cluster inside a fullerene cage, (177)Lu(x)Lu((3-x))N@C(80): an interleukin-13-conjugated radiolabeled metallofullerene platform.

    PubMed

    Shultz, Michael D; Duchamp, James C; Wilson, John D; Shu, Chun-Ying; Ge, Jiechao; Zhang, Jianyuan; Gibson, Harry W; Fillmore, Helen L; Hirsch, Jerry I; Dorn, Harry C; Fatouros, Panos P

    2010-04-14

    In this communication, we describe the successful encapsulation of (177)Lu into the endohedral metallofullerene (177)Lu(x)Lu(3-x)N@C(80) (x = 1-3) starting with (177)LuCl(3) in a modified quartz Kraschmer-Huffman electric generator. We demonstrate that the (177)Lu (beta-emitter) in this fullerene cage is not significantly released for a period of up to at least one-half-life (6.7 days). We also demonstrate that this agent can be conjugated with an interleukin-13 peptide that is designed to target an overexpressed receptor in glioblastoma multiforme tumors. This nanoparticle delivery platform provides flexibility for a wide range of radiotherapeutic and radiodiagnostic multimodal applications.

  10. Photoionization of Au+, Au2+, and Au3+ ions and developments in the synthesis of the metallofullerene Au@C60

    NASA Astrophysics Data System (ADS)

    Kilcoyne, A. L. David; Muller, Alfred; Schippers, Stefan; Hellhund, Jonas; Borovik, Alexander; Mueller, Allison; Gross, Dylan; Johnson, Andrea; Macaluso, David; A. L. D. Kilcoyne Collaboration

    2015-05-01

    Absolute single photoionization of Au+, Au2+, and Au3+ ions was investigated via the merged-beams technique at AMO Beamline 10.0.1.2 of the Advanced Light Source at Lawrence Berkeley National Laboratory. The absolute single photoionization yield was measured as a function of photon energy for each species from the metastable state ionization threshold region to well above the ground state ionization potential. Additional high-resolution measurements were performed for Au+ and Au2+ ions in the region of the ground and metastable state ionization thresholds to better resolve the detailed resonant structure found therein. This structure was used, along with the reported excited state energy levels of Au+, to preliminarily identify previously unreported excitation levels in all three ions. In addition and as a component of the same program, photoionization studies of the endohedral metallofullerene Au@C60+were performed using endohedral fullerene samples synthesized on-site at Beamline 10.0.1.2 of the ALS.

  11. Regioselective benzyl radical addition to an open-shell cluster metallofullerene. Crystallographic studies of cocrystallized Sc3C2@Ih-C80 and its singly bonded derivative.

    PubMed

    Fang, Hongyun; Cong, Hailin; Suzuki, Mitsuaki; Bao, Lipiao; Yu, Bing; Xie, Yunpeng; Mizorogi, Naomi; Olmstead, Marilyn M; Balch, Alan L; Nagase, Shigeru; Akasaka, Takeshi; Lu, Xing

    2014-07-23

    The endohedral fullerene once erroneously identified as Sc3@C82 was recently shown to be Sc3C2@Ih-C80, the first example of an open-shell cluster metallofullerene. We herein report that benzyl bromide (1) reacts with Sc3C2@ Ih-C80 via a regioselective radical addition that affords only one isomer of the adduct Sc3C2@Ih-C80(CH2C6H5) (2) in high yield. An X-ray crystallographic study of 2 demonstrated that the benzyl moiety is singly bonded to the fullerene cage, which eliminates the paramagnetism of the endohedral in agreement with the ESR results. Interestingly, X-ray results further reveal that the 3-fold disordered Sc3C2 cluster adopts two different configurations inside the cage. These configurations represent the so-called "planar" form and the computationally predicted, but not crystallographically characterized, "trifoliate" form. It is noteworthy that this is the first crystallographic observation of the "trifoliate" form for the Sc3C2 cluster. In contrast, crystallographic investigation of a Sc3C2@Ih-C80/Ni(OEP) cocrystal, in which the endohedral persists in an open-shell structure with paramagnetism, indicates that only the former form occurs in pristine Sc3C2@ Ih-C80. These results demonstrate that the cluster configuration in EMFs is highly sensitive to the electronic structure, which is tunable by exohedral modification. In addition, the electrochemical behavior of Sc3C2@Ih-C80 has been markedly changed by the radical addition, but the absorption spectra of the pristine and the derivative are both featureless. These results suggest that the unpaired electron of Sc3C2@Ih-C80 is buried in the Sc3C2 cluster and does not affect the electronic configuration of the cage.

  12. Gd@C82 metallofullerenes for neutron capture therapy—fullerene solubilization by poly(ethylene glycol)-block-poly(2-(N, N-diethylamino)ethyl methacrylate) and resultant efficacy in vitro

    PubMed Central

    Horiguchi, Yukichi; Kudo, Shinpei; Nagasaki, Yukio

    2011-01-01

    Poly(ethylene glycol)-block-poly(2-(N,N-diethylamino)ethyl methacrylate) (PEG-b-PAMA) was found to solubilize fullerenes such as C60, and this technique was applied to metallofullerenes. Gd@C82 was easily dissolved in water in the presence of PEG-b-PAMA without any covalent derivatization, forming a transparent complex about 20–30 nm in diameter. Low cytotoxicity was confirmed in vitro. Neutron irradiation of cultured cells (colon-26 adenocarcinoma) with Gd@C82-PEG-b-PAMA-complexed nanoparticles showed effective cytotoxicity, indicating the effective emission of gamma rays and internal conversion electrons produced from the neutron capture reaction of Gd. This result suggests a potentially valuable approach to gadolinium-based neutron capture therapy. PMID:27877415

  13. Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C 2n, 2n = 74, 82) show cage isomer dependent oxidation states for U† †Electronic supplementary information (ESI) available. CCDC 1508508 1508509 1522558. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01711a Click here for additional data file. Click here for additional data file.

    PubMed Central

    Cai, Wenting; Morales-Martínez, Roser; Zhang, Xingxing; Najera, Daniel; Romero, Elkin L.; Metta-Magaña, Alejandro; Rodríguez-Fortea, Antonio; Fortier, Skye

    2017-01-01

    Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C82, in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@D 3h-C74, U@C 2(5)-C82 and U@C 2v(9)-C82, and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@D 3h-C74 and U@C 2(5)-C82 have tetravalent electronic configurations corresponding to U4+@D 3h-C74 4– and U4+@C 2(5)-C82 4–. Surprisingly, the isomeric U@C 2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C 2v(9)-C82 3–. These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs. PMID:28970908

  14. Self-assembly and alterable relaxivity of an organic cation-encapsulated gadolinium-containing polyoxometalate.

    PubMed

    Wang, Yinglin; Zhou, Shengyan; Kong, Daliang; Yang, Haishan; Chai, Wenqiang; Kortz, Ulrich; Wu, Lixin

    2012-09-07

    A new amphiphilic molecule bearing poly(ethylene oxide) (PEO) and quaternary ammonium group, was designed and synthesized to encapsulate paramagnetic Gd(III)-containing polyoxometalate (Gd-POM) through electrostatic interaction for obtaining a water-soluble organic-inorganic hybrid building block based on POM. The yielding organic cation-encapsulated Gd-POM (OCEP-Gd) complex exhibited water-solubility and amphiphility, leading to the spontaneous self-assembly into a regular vesicular structure with PEO chains towards water phase and POM units locating at the middle. The vesicular aggregate which has a regular monolayer structure, was further studied by means of dynamic light scattering, transmission electron microscopy, and X-ray diffraction. Due to the synergy of different building units, the self-assembly of the complexes was demonstrated to be efficient to adjust the ability of Gd-POM to accelerate relaxation of water-proton, which results from the paramagnetic property of Gd-POM, to a large extent. The present work provides a new methodology to obtain water-soluble hybrid building blocks based on POM, which may generate more hybrid self-assembly structures in aqueous solution and further direct POM-based materials towards biomedical applications.

  15. The isolation of lutetium from gadolinium contained in Purex process solutions

    SciTech Connect

    Bostick, D.T.; Vick, D.O.; May, M.P.; Walker, R.L.

    1992-09-01

    A chemical separation procedure has been devised to isolate Lu from Purex dissolver solutions containing the neutron poison, Gd. The isolation procedure involves the removal of U and >Pu from a dissolver solution using tributylphosphate solvent extraction. If required, solvent extraction using di-(2-ethylhexyl) phosphoric acid can be employed to further purify the sample be removing alkali and alkali earth elements. Finally, Lu is chromatographically separated from Gd and rare earth fission products on a Dowex 50W-X8 resin column using an alpha-hydroxyisobutyrate eluant. The success of the chemical separation procedure has been demonstrated in the quantitative recovery of as little as 1.4 ng Lu from solutions containing a 5000-fold excess of Gd. Additionally, Lu has been isolated from synthetic dissolver samples containing U, Ba, Cs, and Gd. Thermal emission MS data indicated that the Lu fraction of the synthetic sample was free of Gd interference.

  16. The exohedral Diels-Alder reactivity of the titanium carbide endohedral metallofullerene Ti2C2@D(3h)-C78: comparison with D(3h)-C78 and M3N@D(3h)-C78 (M=Sc and Y) reactivity.

    PubMed

    Garcia-Borràs, Marc; Osuna, Sílvia; Luis, Josep M; Swart, Marcel; Solà, Miquel

    2012-06-04

    The chemical functionalization of endohedral (metallo)fullerenes has become a main focus of research in the last few years. It has been found that the reactivity of endohedral (metallo)fullerenes may be quite different from that of the empty fullerenes. Encapsulated species have an enormous influence on the thermodynamics, kinetics, and regiochemistry of the exohedral addition reactions undergone by these species. A detailed understanding of the changes in chemical reactivity due to incarceration of atoms or clusters of atoms is essential to assist the synthesis of new functionalized endohedral fullerenes with specific properties. Herein, we report the study of the Diels-Alder cycloaddition between 1,3-butadiene and all nonequivalent bonds of the Ti(2)C(2)@D(3h)-C(78) metallic carbide endohedral metallofullerene (EMF) at the BP86/TZP//BP86/DZP level of theory. The results obtained are compared with those found by some of us at the same level of theory for the D(3h)-C(78) free cage and the M(3)N@D(3h)-C(78) (M=Sc and Y) metallic nitride EMFs. It is found that the free cage is more reactive than the Ti(2)C(2)@D(3h)-C(78) EMF and this, in turn, has a higher reactivity than M(3)N@D(3h)-C(78). The results indicate that, for Ti(2)C(2)@D(3h)-C(78), the corannulene-type [5,6] bonds c and f, and the type B [6,6] bond 3 are those thermodynamically and kinetically preferred. In contrast, the D(3h)-C(78) free cage has a preference for addition to the [6,6] 1 and 6 bonds and the [5,6] b bond, whereas M(3)N@D(3h)-C(78) favors additions to the [6,6] 6 (M=Sc) and [5,6] d (M=Y) bonds. The reasons for the regioselectivity found in Ti(2)C(2)@D(3h)-C(78) are discussed.

  17. Magnetic properties of rare-earth metallofullerenes

    SciTech Connect

    Funasaka, Hideyuki; Sugiyama, Kenji; Yamamoto, Kazunori; Takahashi, Takeshi )

    1995-02-16

    Bulk amounts of La C[sub 82] and Gd C[sub 82] have been isolated in pure form from various hollow fullerenes. Magnetization data for these powder samples, an isolated La C[sub 82] isomer and a Gd C[sub 82] isomer, have been obtained employing a SQUID magnetometer at temperatures ranging from 3 to 300 K. For La C[sub 82] the inverse susceptibility as a function of temperature follows a Curie-Weiss law. The effective magnetic moment per La C[sub 82] is 0.38 [mu][sub B]. For Gd C[sub 32] the magnetization data fall on a universal curve which is fitted to a Brillouin function in correspondence with the Gd[sup 3+] free ion ground state values of J = 3.38 and g = 2. 33 refs., 6 figs.

  18. Self-assembly of endohedral metallofullerenes: a decisive role of cooling gas and metal–carbon bonding† †Electronic supplementary information (ESI) available: Additional information on metal–carbon bonding and MD simulations. See DOI: 10.1039/c5nr08645k Click here for additional data file.

    PubMed Central

    Deng, Qingming; Heine, Thomas

    2016-01-01

    The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc–C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-T d and Ti@C30-C 2v(3). PMID:26815243

  19. Nanoscale x-ray investigation of magnetic metallofullerene peapods.

    PubMed

    Fritz, Fabian; Westerström, Rasmus; Kostanyan, Aram; Schlesier, Christin; Dreiser, Jan; Watts, Benjamin; Houben, Lothar; Luysberg, Martina; Avdoshenko, Stanislav M; Popov, Alexey A; Schneider, Claus M; Meyer, Carola

    2017-10-27

    Endohedral lanthanide ions packed inside carbon nanotubes (CNTs) in a one-dimensional assembly have been studied with a combination of high resolution transmission electron microscopy (HRTEM), scanning transmission x-ray microscopy (STXM), and x-ray magnetic circular dichroism (XMCD). By correlating HRTEM and STXM images we show that structures down to 30 nm are resolved with chemical contrast and record x-ray absorption spectra from endohedral lanthanide ions embedded in individual nanoscale CNT bundles. XMCD measurements of an Er3N@C80 bulk sample and a macroscopic assembly of filled CNTs indicate that the magnetic properties of the endohedral Er(3+) ions are unchanged when encapsulated in CNTs. This study demonstrates the feasibility of local magnetic x-ray characterisation of low concentrations of lanthanide ions embedded in molecular nanostructures.

  20. Encapsulation of metallofullerenes and metallocenes in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Luzzi, David E.; Smith, Brian W.; Russo, Richard; Satishkumar, B. C.; Stercel, Ferenc; Nemes, Norbert

    2001-11-01

    We encapsulate a number of fullerenes inside single-walled carbon nanotubes (SWNTs) including C60, La2@C80 and ErxSc3-xN@C80(x=0-3). In addition, a number of metallocenes are seen to form hybrid structures with SWNTs, filling the lumen. Ferrocene is used to show that a particular molecule can be induced to fill the lumen of nanotubes from either the liquid or vapor states. The structural properties of these nanoscopic hybrid materials are described using high-resolution transmission electron microscopy (HRTEM) and electron diffraction. It is found that the encapsulated fullerenes self-assemble into long, one-dimensional chains. In the case of C60@SWNT, room-temperature electron diffraction and HRTEM results are consistent with close-packed 1-D chains of equally-spaced monomers.

  1. Hybrid assemblies based on a gadolinium-containing polyoxometalate and a cationic polymer with spermine side chains for enhanced MRI contrast agents.

    PubMed

    Chai, Wenqiang; Wang, Shan; Zhao, Hang; Liu, Guifeng; Fischer, Karl; Li, Haolong; Wu, Lixin; Schmidt, Manfred

    2013-09-27

    Supramolecular assembly: Spherical and stable hybrid assemblies based on a cationic polymer with spermine side chains and an anionic Gd(3+)-containing polyoxometalate cluster (GdW) are prepared by electrostatic interaction. The T1-weighted MRI performance of GdW is enhanced about three times in the assemblies; meanwhile, the assemblies show good biocompatibility, which enables them to be promising candidates for MRI contrast agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Gadolinium-containing magnetic resonance contrast media: investigation on the possible transchelation of Gd³⁺ to the glycosaminoglycan heparin.

    PubMed

    Taupitz, Matthias; Stolzenburg, Nicola; Ebert, Monika; Schnorr, Jörg; Hauptmann, Ralf; Kratz, Harald; Hamm, Bernd; Wagner, Susanne

    2013-01-01

    Retention of gadolinium (Gd) in biological tissues is considered an important cofactor in the development of nephrogenic systemic fibrosis (NSF). Research on this issue has so far focused on the stability of Gd-based contrast media (GdCM) and a possible release of Gd³⁺ from the complex. No studies have investigated competing chelators that may occur in vivo. We performed proton T(1) -relaxometry in solutions of nine approved GdCM and the macromolecular chelator heparin (250 000 IU per 10 ml) without and with addition of ZnCl₂. For the three linear, nonspecific GdCM complexes, Omniscan®, OptiMARK® and Magnevist®, 2 h of incubation in heparin at 37 °C in the presence of 2.0 mm ZnCl₂ led to an increase in T₁-relaxivity by a factor of 7.7, 5.6 and 5.1, respectively. For the three macrocyclic complexes, Gadovist®, Dotarem® and Prohance®, only a minor increase in T₁-relaxivity by a factor of 1.5, 1.6 and 1.7 was found, respectively. Without addition of ZnCl₂, no difference between the two GdCM groups was observed (factors of 1.4, 1.2, 1.1, 1.3, 1.5 and 1.4, respectively). The increase in T₁-relaxivities observed for linear GdCM complexes may be attributable to partial transchelation with formation of a macromolecular Gd-heparin complex. For comparison, mixing of GdCl₃ and heparin results in a 8.7-fold higher T₁-relaxivity compared with a solution of GdCl₃ in water. Heparin is a glycosaminoglycan (GAG) and as such occurs in the human body as a component of the extracellular matrix. GAGs generally are known to be strong chelators. Gd³⁺ released from chelates of GdCM might be complexed by GAGs in vivo, which would explain their retention in biological tissues. Plasma GAG levels are elevated in end-stage renal disease; hence, our results might contribute to the elucidation of NSF.

  3. Physical and electrical properties of trimetallic nitride template endohedral metallofullerenes and their polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Ahmed, Hanaa Mohammed

    The main objective of this study was characterization of pure metallic nitride fullerene, MNF, and MNF containing polymers to evaluate these materials as suitable devices for tunable applications. Polymer-fullerene nanocomposites consisting of linear polyurethane (PU) segments crosslinked via polyhydroxylated fullerenes (C60 and Sc3N C 80, a metallic nitride fullerene) were prepared and characterized for their mechanical and dielectric properties using dynamic mechanical analysis (DMA) and broadband dielectric spectroscopic techniques. Polyhydroxylated fullerenes C60(OH)29 and Sc3N C80(OH) 18 were synthesized in a high yield through a solid-state high sheer ball-milling procedure and were characterized using a verity of techniques, such as FT-R, mass spectroscopy (MS) and thermal gravimetric analysis (TGA), to elucidate their structures. A difunctional isocyanate-terminated prepolymer was prepared from the reaction of poly(tetramethylene oxide) glycol (PTMO, ˜2000 g/mol) and methylene bis(4-isocyanatobenzene) (MDI) followed by the addition of the crosslinking fullerene agent. Fullerene-polymer networks [C60 -PU and Sc3N C80-PU] having high gel fractions and good mechanical properties and thermal stabilities were produced. Dynamic mechanical analyses of (C60 or Sc3N C80)-PU networks indicated a glass transition temperature, Tg, of -50°C with a sub-Tg relaxation due to local chain motions. Broadband dielectric spectroscopic analyses of the nanoparticles prior to incorporation into the networks revealed one relaxation and large epsilon' values in hydroxylated C60 relative to unfunctionalized C60. The analogous hydroxylated Sc3N C80 exhibited two relaxations, and the extra relaxation may be due to reorientations of cage-encapsulated Sc 3N clusters. Permittivity values (epsilon') for Sc3N C 80-PU were found to be higher than the corresponding values for C 60-PU, likely because of the rotationally mobile dipoles. For temperature < 0°C there was a dielectric loss peak due to the glass transition of the PU matrix and another at a lower temperature due to short range chain motions. The loss-frequency spectra of all prepared samples were analyzed sing the Kramers-Kronig transformation and Havriliak-Negami (HN) equation to extract information about relaxation processes taken place in these samples. Capacitance-voltage characteristics of the fullerene-PUs did not show any significant change with the applied dc bias voltage in the range of our instrument window (-30 to +30 volt). A general conclusion is that this class of materials can be rendered quite polarizable.

  4. Metallofullerene nanoparticles promote osteogenic differentiation of bone marrow stromal cells through BMP signaling pathway

    NASA Astrophysics Data System (ADS)

    Yang, Kangning; Cao, Weipeng; Hao, Xiaohong; Xue, Xue; Zhao, Jing; Liu, Juan; Zhao, Yuliang; Meng, Jie; Sun, Baoyun; Zhang, Jinchao; Liang, Xing-Jie

    2013-01-01

    Although endohedral metallofullerenol [Gd@C82(OH)22]n nanoparticles have anti-tumor efficiency and mostly deposit in the bones of mice, how these nanoparticles act in bone marrow stromal cells (MSCs) remains largely unknown. Herein, we observed that [Gd@C82(OH)22]n nanoparticles facilitated the differentiation of MSCs toward osteoblasts, as evidenced by the enhancement of alkaline phosphatase (ALP) activity and mineralized nodule formation upon [Gd@C82(OH)22]n nanoparticle treatment. Mechanistically, the effect of [Gd@C82(OH)22]n nanoparticles on ALP activity was inhibited by the addition of noggin as an inhibitor of the BMP signaling pathway. Moreover, the in vivo results of the ovariectomized rats further indicated that [Gd@C82(OH)22]n nanoparticles effectively improved bone density and prevented osteoporosis.Although endohedral metallofullerenol [Gd@C82(OH)22]n nanoparticles have anti-tumor efficiency and mostly deposit in the bones of mice, how these nanoparticles act in bone marrow stromal cells (MSCs) remains largely unknown. Herein, we observed that [Gd@C82(OH)22]n nanoparticles facilitated the differentiation of MSCs toward osteoblasts, as evidenced by the enhancement of alkaline phosphatase (ALP) activity and mineralized nodule formation upon [Gd@C82(OH)22]n nanoparticle treatment. Mechanistically, the effect of [Gd@C82(OH)22]n nanoparticles on ALP activity was inhibited by the addition of noggin as an inhibitor of the BMP signaling pathway. Moreover, the in vivo results of the ovariectomized rats further indicated that [Gd@C82(OH)22]n nanoparticles effectively improved bone density and prevented osteoporosis. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33575a

  5. Thermoelectricity at the molecular scale: a large Seebeck effect in endohedral metallofullerenes

    NASA Astrophysics Data System (ADS)

    Lee, See Kei; Buerkle, Marius; Yamada, Ryo; Asai, Yoshihiro; Tada, Hirokazu

    2015-12-01

    Single molecule devices provide a unique system to study the thermoelectric energy conversion at an atomistic level and can provide valuable information for the design of organic thermoelectric materials. Here we present a comprehensive study of the thermoelectric transport properties of molecular junctions based on C82, Gd@C82, and Ce@C82. We combine precise scanning tunneling microscope break-junction measurements of the thermopower and conductance with quantitatively accurate self-energy-corrected first-principles transport calculations. We find that all three fullerene derivatives give rise to a negative thermopower (n-conducting). The absolute value, however, is much larger for the Gd@C82 and Ce@C82 junctions. The conductance, on the other hand, remains comparable for all three systems. The power factor determined for the Gd@C82 based junction is so far the highest obtained for a single-molecule device. Although the encapsulated metal atom does not directly contribute to the transport, we show that the observed enhancement of the thermopower for Gd@C82 and Ce@C82 is elucidated by the substantial changes in the electronic- and geometrical structure of the fullerene molecule induced by the encapsulated metal atom.Single molecule devices provide a unique system to study the thermoelectric energy conversion at an atomistic level and can provide valuable information for the design of organic thermoelectric materials. Here we present a comprehensive study of the thermoelectric transport properties of molecular junctions based on C82, Gd@C82, and Ce@C82. We combine precise scanning tunneling microscope break-junction measurements of the thermopower and conductance with quantitatively accurate self-energy-corrected first-principles transport calculations. We find that all three fullerene derivatives give rise to a negative thermopower (n-conducting). The absolute value, however, is much larger for the Gd@C82 and Ce@C82 junctions. The conductance, on the other hand, remains comparable for all three systems. The power factor determined for the Gd@C82 based junction is so far the highest obtained for a single-molecule device. Although the encapsulated metal atom does not directly contribute to the transport, we show that the observed enhancement of the thermopower for Gd@C82 and Ce@C82 is elucidated by the substantial changes in the electronic- and geometrical structure of the fullerene molecule induced by the encapsulated metal atom. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05394c

  6. Thermoelectricity at the molecular scale: a large Seebeck effect in endohedral metallofullerenes.

    PubMed

    Lee, See Kei; Buerkle, Marius; Yamada, Ryo; Asai, Yoshihiro; Tada, Hirokazu

    2015-12-28

    Single molecule devices provide a unique system to study the thermoelectric energy conversion at an atomistic level and can provide valuable information for the design of organic thermoelectric materials. Here we present a comprehensive study of the thermoelectric transport properties of molecular junctions based on C(82), Gd@C(82), and Ce@C(82). We combine precise scanning tunneling microscope break-junction measurements of the thermopower and conductance with quantitatively accurate self-energy-corrected first-principles transport calculations. We find that all three fullerene derivatives give rise to a negative thermopower (n-conducting). The absolute value, however, is much larger for the Gd@C(82) and Ce@C(82) junctions. The conductance, on the other hand, remains comparable for all three systems. The power factor determined for the Gd@C(82) based junction is so far the highest obtained for a single-molecule device. Although the encapsulated metal atom does not directly contribute to the transport, we show that the observed enhancement of the thermopower for Gd@C(82) and Ce@C(82) is elucidated by the substantial changes in the electronic- and geometrical structure of the fullerene molecule induced by the encapsulated metal atom.

  7. In-Plane Intermolecular Interaction Assisted Assembly and Modified Electronic States of Metallofullerene Gd@C₈₂.

    PubMed

    Chen, Jian; Qin, Zhihui; Pan, Jinbo; Huang, Min; Du, Shixuan; Cao, Gengyu

    2015-10-27

    Orientational configuration and electronic states of Gd@C82 bonding to Cu(111) have been thoroughly investigated by low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/S) and differential conductance mapping complemented by first-principles calculations. We clarify that individual Gd@C82 energetically adopts tilting adsorption configuration with the scanning tunneling spectroscopy (STS) states readily assigned to the C82 cage/Cu(111) hybrid states and the Gd/cage hybrid states, respectively. Moreover, upon assembling and sufficient thermal activation, Gd@C82 fullerenes are inclined to restore the energetically favored tilting orientational configuration similar to an individual one. This suggests the feasibility of high-level integration of single-Gd@C82 based moletronic device with the performances almost unchanged by two-dimensional arrangement. Furthermore, by rationalizing the inter-Gd@C82 interaction induced slight energy offset of the electronic states, we qualitatively confirm the shown electronic hybrid states as Cu(111)-, C82 cage- and Gd-dominant hybrid states, respectively.

  8. Small endohedral metallofullerenes: exploration of the structure and growth mechanism in the Ti@C2n (2n = 26-50) family.

    PubMed

    Mulet-Gas, Marc; Abella, Laura; Dunk, Paul W; Rodríguez-Fortea, Antonio; Kroto, Harold W; Poblet, Josep M

    2015-01-01

    The formation of the smallest fullerene, C28, was recently reported using gas phase experiments combined with high-resolution FT-ICR mass spectrometry. An internally located group IV metal stabilizes the highly strained non-IPR C28 cage by charge transfer (IPR = isolated pentagon rule). Ti@C44 also appeared as a prominent peak in the mass spectra, and U@C28 was demonstrated to form by a bottom-up growth mechanism. We report here a computational analysis using standard DFT calculations and Car-Parrinello MD simulations for the family of the titled compounds, aiming to identify the optimal cage for each endohedral fullerene and to unravel key aspects of the intriguing growth mechanisms of fullerenes. We show that all the optimal isomers from C26 to C50 are linked by a simple C2 insertion, with the exception of a few carbon cages that require an additional C2 rearrangement. The ingestion of a C2 unit is always an exergonic/exothermic process that can occur through a rather simple mechanism, with the most energetically demanding step corresponding to the closure of the carbon cage. The large formation abundance observed in mass spectra for Ti@C28 and Ti@C44 can be explained by the special electronic properties of these cages and their higher relative stabilities with respect to C2 reactivity. We further verify that extrusion of C atoms from an already closed fullerene is much more energetically demanding than forming the fullerene by a bottom-up mechanism. Independent of the formation mechanism, the present investigations strongly support that, among all the possible isomers, the most stable, smaller non-IPR carbon cages are formed, a conclusion that is also valid for medium and large cages.

  9. M2@C79N (M = Y, Tb): Isolation and Characterization of Stable Endohedral Metallofullerenes Exhibiting M-M Bonding Interactions Inside Aza[80]Fullerene Cages

    PubMed Central

    Zuo, Tianming; Xu, Liaosa; Beavers, Christine M.; Olmstead, Marilyn M.; Fu, Wujun; Crawford, T. Daniel; Dorn, Harry C.

    2009-01-01

    Y2@C79N and Tb2@C79N have been prepared by conducting the Krätschmer-Huffman electric arc-process under 20 torr of N2 and 280 torr of He with metal oxide doped graphite rods. These new heterofullerenes were separated from the resulting mixture of empty cage fullerenes and endohedral fullerenes by chemical separation and a two stage chromatographic process. Crystallographic data for Tb2@C79N • Ni(OEP) • 2C6H6 demonstrate the presence of an 80-atom cage with idealized Ih symmetry and two, widely separated Tb atoms inside with a Tb---Tb separation of 3.9020(10) Å for the major terbium sites. The EPR spectrum of the odd-electron Y2@C79N indicates that the spin density largely resides on the two, equivalent yttrium ions. Computational studies on Y2@C79N suggest that the nitrogen atom resides at a 665 ring junction in the equator on the fullerene cage and that the unpaired electron is localized in a bonding orbital between the two yttrium ions of this stable radical. Thus, the Tb-Tb bond length of the single-electron bond is the longest metal-metal bond reported so far. PMID:18774804

  10. Quantum-chemical calculations of the metallofullerene yields in the X@C{sub 74}, L@C{sub 74}, and Z@C{sub 82} series

    SciTech Connect

    Uhlík, Filip; Slanina, Zdeněk; Nagase, Shigeru

    2015-01-22

    The contribution reports computations for Al@C{sub 82}, Sc@C{sub 82}, Y@C{sub 82} and La@C{sub 82} based on encapsulation into the IPR (isolated pentagon rule) C{sub 2ν} C{sub 82} cage and also on Mg@C{sub 74}, Ca@C{sub 74}, Sr@C{sub 74} and Ba@C{sub 74} based on encapsulation into the only C{sub 74} IPR cage as well as for three selected lanthanoids La@C{sub 74}, Yb@C{sub 74}, and Lu@C{sub 74}. Their structural and energetic characteristics are used for evaluations of the relative production yields, using the encapsulation Gibbs-energy and saturated metal pressures. It is shown that the results can be well related to the ionization potentials of the free metal atoms.

  11. Effect of encapsulation (Ru & Pd) small clusters in fullerene (C60) on electronic and magnetic properties: DFT

    NASA Astrophysics Data System (ADS)

    Abdaljalil, Rana. O.; Umran, Nibras. M.

    2017-09-01

    We have done a systematic study of structural and electronic, to describe the Interaction between various atoms doped inside C60 by using Density functional theory (DFT). The foresee for carbon doping, modifies the electronic properties of fullerenes. We optimized the Run@C60 and Pdn@C60 (n=1-4) complexes, we found that endohedral metallofullerenes are stable. As well, we investigated binding energy, ionization potential, and energy gap of Ru and Pd encapsulate fullerenes. Where observed the effect modified by endohedral metallofullerenes makes C60 more reactive. Also the presence of the magnetic moment in metallofullerenes using Mulliken charge analysis.

  12. Design parameters for carbon nanobottles to absorb and store methane.

    PubMed

    Lee, Richard K F; Hill, James M

    2011-08-01

    We investigate the internal mechanics for methane storage in a nanobottle, which is assumed to comprise a metallofullerene located inside a carbon nanobottle, which is constructed from a half-fullerene as the base, and two nanotubes which are joined by a nanocone. The interaction potential energy for the metallofullerene is obtained from the 6-12 Lennard-Jones potential and the continuum approximation, which assumes that a discrete atomic structure can be replaced by an average atomic surface density. This potential energy shows that the metallofullerene has two minimum energy positions, which are located close to the neck of the bottle and at the base of the nanobottle, and therefore it may be used as a bottle-stopper to open or to close the nanobottle. At the neck of the bottle, the encapsulated metallofullerene closes the nanobottle, and by applying an external electrical force, the metallofullerene can overcome the energy barrier of the nanotube, and pass from the neck of the nanobottle to the base so that the nanobottle is open. For methane storage, the metallofullerene serves the dual purposes of opening and closing the nanobottle, as well as an attractor for the methane gas. The analytical formulation gives rise to a rapid computational capacity, and enables the direct determination of the optimal dimensions necessary to ensure the correct working function of the nanobottle, and specific ranges for the critical parameters are formulated.

  13. Biomedical Applications of Metal-Encapsulated Fullerene Nanoparticles.

    PubMed

    Li, Tinghui; Dorn, Harry C

    2017-02-01

    The carbonaceous nanomaterials known as metallofullerenes have attracted considerable attention due to their attractive properties. The robust nature of the "Trojan Horse" fullerene cage provides an important structural component, which isolates the metal cluster from the bioenvironment. The large carbon surface area is ideally suited for multiple exo-functionalization approaches to modify the hydrophobic cage for a more hydrophilic bioenvironment. Additionally, peptides and other agents are readily covalently attached to this nanoprobe for targeting applications. The recent progress in developing metallofullerenes for next-generation biomedical applications is described. Of special interest are magnetic resonance imaging (MRI) contrast agents. Several recent studies reported cumulative gadolinium deposition in the brain and bones of individuals using commercial clinical MRI contrast agents. Gadolinium-based metallofullerenes provide 2-3 orders of magnitude improvement in MRI relaxivity and potentially lower clinical levels of toxic Gd(3+) ions deposited. Other potential biomedical applications are also reviewed herein.

  14. [Indications and contraindications for contrast-enhanced MRI and CT during pregnancy].

    PubMed

    Junkermann, H

    2007-09-01

    There are no reports about negative effects on the fetus of the application of gadolinium-containing contrast media to pregnant mothers. Iodine-containing contrast media may lead to a transient hypothyroidism in the newborn. This will be detected with certainty by the neonatal TSH screening. Iodine- or gadolinium-containing contrast media may be used in pregnant women if indispensable. In the gut of breastfed children less than 1% of the recommended pediatric doses of contrast media are found after both types of contrast media have been given to their mothers. Therefore there are no reasons against the use of contrast media during the nursing period.

  15. Gadolinium deposition in nephrogenic fibrosing dermopathy.

    PubMed

    Boyd, Alan S; Zic, John A; Abraham, Jerrold L

    2007-01-01

    There is growing recognition of the association between the use of gadolinium-containing radiocontrast agents for magnetic resonance imaging and the serious dermal and systemic disease nephrogenic fibrosing dermopathy/nephrogenic systemic fibrosis (NFD/NSF). The pathogenesis of this entity remains unclear; however, our recent observations suggest a likely mechanism for the initial dermal manifestations of this gadolinium toxicity.

  16. Allergic-like breakthrough reactions to gadolinium contrast agents after corticosteroid and antihistamine premedication.

    PubMed

    Dillman, Jonathan R; Ellis, James H; Cohan, Richard H; Strouse, Peter J; Jan, Sophia C

    2008-01-01

    The objective of our study was to determine the number and severity of allergic-like breakthrough reactions to i.v. gadolinium-containing contrast agents in children and adults after premedication with corticosteroids and antihistamines. Contrast material reaction forms from the department of radiology for pediatric (under 19 years old) and adult patients were reviewed for the time period from January 1, 2001, through December 31, 2006. All documented allergic-like reactions to i.v. gadolinium-containing contrast media after premedication with corticosteroids and antihistamines were identified. Forms were evaluated for reaction manifestations, management, and patient outcome. Our institutional electronic medical record system was accessed for each individual patient to identify pertinent medical history, including demographic information, history of allergic-like reaction to contrast media (gadolinium- or iodine-containing), and additional factors that led to prophylactic premedication. Eight patients experienced nine allergic-like reactions after the i.v. administration of gadolinium-containing contrast media despite premedication. A single patient had two breakthrough reactions. Six breakthrough reactions were mild, and three were moderate. No severe or fatal breakthrough reaction occurred. Eight of nine breakthrough reactions occurred in adults. All patients who experienced breakthrough reactions had a history of allergic-like reaction to either gadolinium- or iodine-containing contrast media. Allergic-like reactions to gadolinium-containing contrast media can occur despite premedication with corticosteroids and antihistamines.

  17. Small endohedral metallofullerenes: exploration of the structure and growth mechanism in the Ti@C2n (2n = 26–50) family† †Electronic supplementary information (ESI) available: additional figures of energy profiles, detailed information about the Car–Parrinello simulations (including two movies) and optimized geometries for the most representative structures. See DOI: 10.1039/c4sc02268h Click here for additional data file. Click here for additional data file. Click here for additional data file.

    PubMed Central

    Mulet-Gas, Marc; Abella, Laura; Dunk, Paul W.

    2015-01-01

    The formation of the smallest fullerene, C28, was recently reported using gas phase experiments combined with high-resolution FT-ICR mass spectrometry. An internally located group IV metal stabilizes the highly strained non-IPR C28 cage by charge transfer (IPR = isolated pentagon rule). Ti@C44 also appeared as a prominent peak in the mass spectra, and U@C28 was demonstrated to form by a bottom-up growth mechanism. We report here a computational analysis using standard DFT calculations and Car–Parrinello MD simulations for the family of the titled compounds, aiming to identify the optimal cage for each endohedral fullerene and to unravel key aspects of the intriguing growth mechanisms of fullerenes. We show that all the optimal isomers from C26 to C50 are linked by a simple C2 insertion, with the exception of a few carbon cages that require an additional C2 rearrangement. The ingestion of a C2 unit is always an exergonic/exothermic process that can occur through a rather simple mechanism, with the most energetically demanding step corresponding to the closure of the carbon cage. The large formation abundance observed in mass spectra for Ti@C28 and Ti@C44 can be explained by the special electronic properties of these cages and their higher relative stabilities with respect to C2 reactivity. We further verify that extrusion of C atoms from an already closed fullerene is much more energetically demanding than forming the fullerene by a bottom-up mechanism. Independent of the formation mechanism, the present investigations strongly support that, among all the possible isomers, the most stable, smaller non-IPR carbon cages are formed, a conclusion that is also valid for medium and large cages. PMID:28936315

  18. Understanding the stabilization of metal carbide endohedral fullerenes M2C2@C82 and related systems.

    PubMed

    Valencia, Ramón; Rodríguez-Fortea, Antonio; Poblet, Josep M

    2008-05-22

    We analyze the electronic structure of carbide endohedral metallofullerenes of the type Sc(2)C(2)@C(82) and study the possibility of rotation of the encapsulated Sc(2)C(2) moiety in the interior of the cage. Moreover, we rationalize the higher abundance of M(2)C(2)@C(82) (M = Sc, Y) in which the metal-carbide cluster is encapsulated in the C(3v)-C(82):8 carbon cage with respect to other carbides of the same family on the basis of the formal transfer of four electrons from the cluster to the cage and sizeable (LUMO-3)-(LUMO-2) gap in the empty cages. This rule also applies to all those endohedral metallofullerenes in which the encapsulated cluster transfers four electrons to the carbon cage as, for example, the reduced [M@C(82)](-) systems (M = group 3 or lanthanide metal ion).

  19. Theoretical prediction of the structures and properties of metal sulfide fullerene Sc2S@C80

    NASA Astrophysics Data System (ADS)

    Gan, Li-Hua; Lei, Dan; Zhao, Chong; Guo, Xiao

    2014-06-01

    Sc2S@C80 has been detected but not been isolated and characterized. To investigate the structures and properties of Sc2S@C80, a density functional theory study on fullerene C80 and metallofullerene Sc2S@C80 was carried out. The calculations demonstrate that Sc2S prefers to be encapsulated inside D5h-C80 and C2v-C80, instead of the well-known Ih-C80. The two lowest-energy isomers of Sc2S@C80 may coexist in the soot. The calculations reveal that there exists strong covalent interaction between the cage and Sc2S cluster, suggesting Sc2S@C80 may have different properties from those usual C80-based metallofullerenes. Raman spectra are provided to help future experimental identification of Sc2S@C80.

  20. Explosion Production of Fullerenes from Carbonaceous Bullet in Vacuum Using Rail Gun

    NASA Astrophysics Data System (ADS)

    Mieno, Tetsu; Yamori, Akira

    2006-04-01

    A carbonaceous bullet is accelerated using a rail gun in vacuum and collides with a metal or carbon target at a speed of approximately 6 km/s, at which the bullet explodes and the high-temperature reaction of carbon particles takes place. As a result, C60 and higher fullerenes are produced. Using a carbonaceous bullet containing metal-oxide powder, endohedral metallofullerenes are also produced by this method.

  1. Defect Induced Electronic Structure of Uranofullerene

    PubMed Central

    Dai, Xing; Cheng, Cheng; Zhang, Wei; Xin, Minsi; Huai, Ping; Zhang, Ruiqin; Wang, Zhigang

    2013-01-01

    The interaction between the inner atoms/cluster and the outer fullerene cage is the source of various novel properties of endohedral metallofullerenes. Herein, we introduce an adatom-type spin polarization defect on the surface of a typical endohedral stable U2@C60 to predict the associated structure and electronic properties of U2@C61 based on the density functional theory method. We found that defect induces obvious changes in the electronic structure of this metallofullerene. More interestingly, the ground state of U2@C61 is nonet spin in contrast to the septet of U2@C60. Electronic structure analysis shows that the inner U atoms and the C ad-atom on the surface of the cage contribute together to this spin state, which is brought about by a ferromagnetic coupling between the spin of the unpaired electrons of the U atoms and the C ad-atom. This discovery may provide a possible approach to adapt the electronic structure properties of endohedral metallofullerenes. PMID:23439318

  2. [Nephrogenic systemic fibrosis. Medical detective work in the 21st century].

    PubMed

    Manger, B

    2007-10-01

    Nephrogenic systemic fibrosis is a new disease entity which was first described in 2000. It is characterized by dermal and visceral fibrosis in patients with impaired renal function. Recently, the etiology of this disease has been unveiled. The application of gadolinium-containing contrast media in patients with decreased renal function can lead to gadolinium deposition in various tissues which induces the fibrotic process. Numerous publications within the last few months have supported this hypothesis and have led to recommendations by the health authorities to carefully weigh the benefits and risks of using gadolinium in patients with impaired renal function.

  3. Fate and toxicity of metallic and metal-containing nanoparticles for biomedical applications.

    PubMed

    Li, Yu-Feng; Chen, Chunying

    2011-11-04

    It is important to obtain a better understanding of the uptake, trafficking, pharmacokinetics, clearance, and role of nanomaterials in biological systems, so that their possible undesirable effects can be avoided. A number of metallic or metal-containing nanomaterials, such as gold nanoparticles and nanorods, quantum dots, iron oxides nanoparticles, and endohedral metallofullerenes, have already been or will soon become very promising for biomedical applications. This review presents a summary of currently available data on the fate and toxicity of these metallic or metal-containing nanoparticles based on animal studies. Several issues regarding the nanotoxicity assessment and future directions on the study of the fate of these nanoparticles are also proposed.

  4. Molecular dynamical modelling of endohedral fullerenes formation in plasma

    NASA Astrophysics Data System (ADS)

    Fedorov, A. S.; Kovaleva, E. A.; Lubkova, T. A.; Popov, Z. I.; Kuzubov, A. A.; Visotin, M. A.; Irle, S.

    2016-02-01

    The initial stages of fullerene and endohedral metallofullerene (EMF) synthesis in carbon-helium plasma at 1500 K and 2500 K have been simulated with quantum chemical molecular dynamics (MD) based on density-functional tight-binding (DFTB). The cases of formation of large (>100 atoms) sp2-carbon clusters with scandium atoms inside were observed. These clusters are considered as precursors of fullerenes or EMFs, and thus it is shown that formation of EMFs can be explained within the framework of "shrinking hot giant" mechanism. Also, the dependence of formation rates on plasma parameters, including temperature, buffer gas and metal atoms concentrations, has been studied.

  5. Application of extracellular gadolinium-based MRI contrast agents and the risk of nephrogenic systemic fibrosis.

    PubMed

    Heverhagen, J T; Krombach, G A; Gizewski, E

    2014-07-01

    Nephrogenic systemic fibrosis (NSF) is a serious, sometimes fatal disease. Findings in recent years have shown that a causal association between gadolinium containing contrast media and NSF is most likely. Therefore, the regulatory authorities have issued guidelines on the use of gadolinium-containing contrast media which have reduced the number of new cases of NSF to almost zero. However, it is for precisely this reason that the greatest care must still be taken to ensure that these guidelines are complied with. The most important factors are renal function, the quantity of gadolinium administered and coexisting diseases such as inflammation. All of these factors crucially influence the quantity of gadolinium released from the chelat in the body. This free gadolinium is thought to be the trigger for NSF. Other important factors are the stability of the gadolinium complex and furthermore the route of its elimination from the body. Partial elimination via the liver might be an additional protective mechanism. In conclusion, despite the NSF risk, contrast-enhanced MRI is a safe diagnostic procedure which can be used reliably and safely even in patients with severe renal failure, and does not necessarily have to be replaced by other methods.

  6. NEPHROGENIC SYSTEMIC FIBROSIS: CURRENT CONCEPTS

    PubMed Central

    Basak, Prasanta; Jesmajian, Stephen

    2011-01-01

    Nephrogenic systemic fibrosis (NSF) was first described in 2000 as a scleromyxedema-like illness in patients on chronic hemodialysis. The relationship between NSF and gadolinium contrast during magnetic resonance imaging was postulated in 2006, and subsequently, virtually all published cases of NSF have had documented prior exposure to gadolinium-containing contrast agents. NSF has been reported in patients from a variety of ethnic backgrounds from America, Europe, Asia and Australia. Skin lesions may evolve into poorly demarcated thickened plaques that range from erythematous to hyperpigmented. With time, the skin becomes markedly indurated and tethered to the underlying fascia. Extracutaneous manifestations also occur. The diagnosis of NSF is based on the presence of characteristic clinical features in the setting of chronic kidney disease, and substantiated by skin histology. Differential diagnosis is with scleroderma, scleredema, scleromyxedema, graft-versus-host disease, etc. NSF has a relentlessly progressive course. While there is no consistently successful treatment for NSF, improving renal function seems to slow or arrest the progression of this condition. Because essentially all cases of NSF have developed following exposure to a gadolinium-containing contrast agent, prevention of this devastating condition involves the careful avoidance of administering these agents to individuals at risk. PMID:21572795

  7. [Nephrogenic systemic fibrosis].

    PubMed

    Artunc, F; Schanz, S; Metze, D; Heyne, N

    2008-01-01

    Nephrogenic systemic fibrosis (NSF) is a novel disease entity, increasingly diagnosed over the last years in patients with renal functional impairment and chronic kidney disease. Recently, gadolinium-containing MR contrast agents have been causally associated with the development NSF. Herein, we present the case of a dialysis-dependent young patient with systemic lupus erythematodes, who developed disabling cutaneous sclerosis of extremities, abdomen and mammae. Clinical and laboratory investigations revealed no signs of activity of the underlying disease. Histopathological examination of a skin biopsy was consistent with NSF showing profound thickening of tissue septae with mucine deposition and slight fibroblast proliferation without inflammatory reaction. Analysis of the patient's medical history revealed that she had undergone repeated contrast enhanced MR scans, including MR angiographies with high doses of gadopentetate. UV phototherapy was little effective, and not until kidney transplantation two years later with good allograft function, improvement of clinical symptoms was observed. Discussion of this case summarizes the current knowledge of clinical features and pathogeneses of NSF, including the role of gadolinium-containing contrast agents. Evolving clinical implications are summarized in the current Tübingen University Hospital guideline for the use of contrast-enhanced MR scans in patients with impaired renal function.

  8. Cage-Core Interactions in Fullerenes Enclosing Metal Clusters with Multiple Scandium and Yttrium Atoms.

    NASA Astrophysics Data System (ADS)

    Dan, Liu; Hagelberg, Frank

    2007-03-01

    Pronounced stability has been reported for metallofullerenes of the form NSc3@CN (N = 68, 78) /1/. In response of these and related findings, Density Functional Theory studies have been performed on the relation between cage-core interactions and the geometry as well as stability of endofullerenes with metal impurities containing Sc and Y. Substantial electron transfer from the metal core to the fullerene cage combines with electron backdonation, involving the interaction between the occupied orbitals of the negatively charged cage and the unoccupied d orbitals of the positively charged core. The Hueckel 4n+2 rule, well established in organic chemistry, is shown to provide a valuable heuristic tool for understanding the intramolecular electron transfer and the related stability gain /1/. The usefulness of the aromaticity concept for explaining and predicting the architecture of metallofullerenes is further exemplified by the units Sc2@C84 and Y2@C84 which were analyzed in spin triplet and singlet conditions. The Sc2 core turns out to be realized by two separated ions, while Y2 forms a bound subunit. These findings are in agreement with conclusions based on the 4n + 2 rule, assisted by Nucleus Independent Chemical Shift (NICS) calculations. /1/ Stevenson, S.; Fowler, P.W.; Heine, T.; Duchamp, J.C.; Rice, G.; Glass, T.; Harich, K.; Hadju, F.; Bible, R.; Dorn, H.C. Nature, 2000, 408, 427, /2/ S. S. Park, D. Liu, F. Hagelberg, J. Phys. Chem. A 109, 8865 (2005).

  9. A density functional theory investigation for the open-shell metal-carbide endofullerene Lu3C2@C88(D2:35) and closed-shell metal-nitride endofullerene Lu3N@C88(D2:35).

    PubMed

    Wu, Jing-Yi; Xu, Wei; Wang, Tai-Shan; Jiang, Li; Shu, Chun-Ying; Wang, Chun-Ru

    2012-03-01

    By means of the density functional theory calculations, two C88(D2:35)-based endohedral fullerenes, Lu3C2@C88(D2:35) and Lu3N@C88(D2:35) which encapsulate tri-lutetium carbide and tri-lutetium nitride cluster were investigated. For the cores in Lu3C2@C88 and Lu3N@C88, the trivalent C2 and N respectively template a butterfly-shaped endohedral moiety and a planar tri-lutetium cluster within the same D2-symmetric C88 cage. Moreover, Lu3N@C88 - D2 has a closed-shell electronic structure but for LuC3C2@C88 - D2, it owns an unpaired electron mainly localized on the internal Lu3C2 cluster. These results clearly showed that the core unit C2(3) as well as N3- play an important role in constructing molecular structures and electronic features of metallofullerenes. Furthermore, the electrochemical redox potentials, and vibrational frequencies of the two endofullerenes agree well with our experimental results. The electronic structures, ionization energies, electron affinities, inner clusters' dynamic motions of them have been predicted to further disclose the characters of these two metallofullerenes.

  10. Facile Preparation of a New Gadofullerene-Based Magnetic Resonance Imaging Contrast Agent with High 1H Relaxivity

    PubMed Central

    Shu, Chunying; Corwin, Frank D.; Zhang, Jianfei; Chen, Zhijian; Reid, Jonathan E.; Sun, Minghao; Xu, Wei; Sim, Jae Hyun; Wang, Chunru; Fatouros, Panos P.; Esker, Alan R.; Gibson, Harry W.; Dorn, Harry C.

    2009-01-01

    A new magnetic resonance imaging (MRI) contrast agent based on the trimetallic nitride templated (TNT) metallofullerene, Gd3N@C80, was synthesized by a facile method in high yield. The observed longitudinal and transverse relaxivities, r1 and r2, for water hydrogens in the presence of the water-soluble gadofullerene 2, Gd3N@C80(OH)~26(CH2CH2COOM)~16 (M = Na or H), are 207 and 282 mM-1s-1 (per C80 cage) at 2.4 T, respectively; these values are 50 times larger than those of Gd3+ poly(aminocarboxylate) complexes, such as commercial Omniscan® and Magnevist®. This high 1H relaxivity for this new hydroxylated and carboxylated gadofullerene derivative provides high signal enhancement at significantly lower Gd concentration as demonstrated by in vitro and in vivo MRI studies. Dynamic light scattering data reveal a unimodal size distribution with an average hydrodynamic radius of ca. 78 nm in pure water (pH = 7), which is significantly different from other hydroxylated or carboxylated fullerene and metallofullerene derivatives reported to date. Agarose gel infusion results indicate that the gadofullerene 2 displayed diffusion properties different from that of commercial Omniscan® and those of PEG5000 modified Gd3N@C80. The reactive carboxyl functionality present on this highly efficient contrast agent may also serve as a precursor for biomarker tissue-targeting purposes. PMID:19445504

  11. Nanoscale fullerene compression of an yttrium carbide cluster.

    PubMed

    Zhang, Jianyuan; Fuhrer, Tim; Fu, Wujun; Ge, Jiechao; Bearden, Daniel W; Dallas, Jerry; Duchamp, James; Walker, Kenneth; Champion, Hunter; Azurmendi, Hugo; Harich, Kim; Dorn, Harry C

    2012-05-23

    The nanoscale parameters of metal clusters and lattices have a crucial influence on the macroscopic properties of materials. Herein, we provide a detailed study on the size and shape of isolated yttrium carbide clusters in different fullerene cages. A family of diyttrium endohedral metallofullerenes with the general formula of Y(2)C(2n) (n = 40-59) are reported. The high field (13)C nuclear magnetic resonance (NMR) and density functional theory (DFT) methods are employed to examine this yttrium carbide cluster in certain family members, Y(2)C(2)@D(5)(450)-C(100), Y(2)C(2)@D(3)(85)-C(92), Y(2)C(2)@C(84), Y(2)C(2)@C(3v)(8)-C(82), and Y(2)C(2)@C(s)(6)-C(82). The results of this study suggest that decreasing the size of a fullerene cage with the same (Y(2)C(2))(4+) cluster results in nanoscale fullerene compression (NFC) from a nearly linear stretched geometry to a constrained "butterfly" structure. The (13)C NMR chemical shift and scalar (1)J(YC) coupling parameters provide a very sensitive measure of this NFC effect for the (Y(2)C(2))(4+) cluster. The crystal structural parameters of a previously reported metal carbide, Y(2)C(3) are directly compared to the (Y(2)C(2))(4+) cluster in the current metallofullerene study.

  12. On the formation of smaller p-block endohedral fullerenes: Bonding analysis in the E@C20 (E = Si, Ge, Sn, Pb) series from relativistic DFT calculations.

    PubMed

    Muñoz-Castro, Alvaro; King, R Bruce

    2017-07-15

    Experimentally characterized endohedral metallofullerenes are of current interest in expanding the range of viable fullerenic structures and their applications. Smaller metallofullerenes, such as M@C28 , show that several d- and f-block elements can be efficiently confined in relatively small carbon cages. This article explores the potential capabilities of the smallest fullerene cage, that is, C20 , to encapsulate p-block elements from group 14, that is, E = Si, Ge, Sn, and Pb. Our interest relates to the bonding features and optical properties related to E@C20 . The results indicate both s- and p-type concentric bonds, in contrast to the well explored endohedral structures encapsulating f-block elements. Our results suggest the E@C20 series to be a new family of viable endohedral fullerenes. In addition spectroscopic properties related to electron affinity, optical, and vibrational were modeled to gain further information useful for characterization. Characteristic optical patterns were studied predicting a distinctive first peak located between 400 and 250 nm, which is red-shifted going to the heavier encapsulated Group 14 atoms. Electron affinity properties expose different patterns useful to differentiate the hollow C20 fullerene to the proposed p-block endohedral counterparts. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  13. Metal nitride cluster fullerene M3N@C80 (M=Y, Sc) based dyads: synthesis, and electrochemical, theoretical and photophysical studies.

    PubMed

    Pinzón, Julio R; Cardona, Claudia M; Herranz, Maria Angeles; Plonska-Brzezinska, Marta E; Palkar, Amit; Athans, Andreas J; Martín, Nazario; Rodríguez-Fortea, Antonio; Poblet, Josep M; Bottari, Giovanni; Torres, Tomás; Gayathri, S Shankara; Guldi, Dirk M; Echegoyen, Luis

    2009-01-01

    The first pyrrolidine and cyclopropane derivatives of the trimetallic nitride templated (TNT) endohedral metallofullerenes I(h)-Sc(3)N@C(80) and I(h)-Y(3)N@C(80) connected to an electron-donor unit (i.e., tetrathiafulvalene, phthalocyanine or ferrocene) were successfully prepared by 1,3-dipolar cycloaddition reactions of azomethine ylides and Bingel-Hirsch-type reactions. Electrochemical studies confirmed the formation of the [6,6] regioisomers for the Y(3)N@C(80)-based dyads and the [5,6] regioisomers in the case of Sc(3)N@C(80)-based dyads. Similar to other TNT endohedral metallofullerene systems previously synthesized, irreversible reductive behavior was observed for the [6,6]-Y(3)N@C(80)-based dyads, whereas the [5,6]-Sc(3)N@C(80)-based dyads exhibited reversible reductive electrochemistry. Density functional calculations were also carried out on these dyads confirming the importance of these structures as electron transfer model systems. Furthermore, photophysical investigations on a ferrocenyl-Sc(3)N@C(80)-fulleropyrrolidine dyad demonstrated the existence of a photoinduced electron-transfer process that yields a radical ion pair with a lifetime three times longer than that obtained for the analogous C(60) dyad.

  14. Release of metal impurities from carbon nanomaterials influences aquatic toxicity.

    PubMed

    Hull, Matthew S; Kennedy, Alan J; Steevens, Jeffery A; Bednar, Anthony J; Weiss, Charles A; Vikesland, Peter J

    2009-06-01

    Few studies have considered the environmental impacts of impurities and byproducts associated with low-efficiency nanomanufacturing processes. Here, we study the composition and aquatic toxicity of low-purity, as-produced fullerenes (C60) and metallofullerene waste solids, both of which were generated via arc-discharge synthesis. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) and inductively coupled plasma mass spectroscopy (ICP-MS) were used to characterize the metals composition of the solid test materials and of aqueous leachates prepared by mixing test materials with waters of varying pH, hardness, and salinity. The aquatic toxicity of the leachates was determined using U.S. Environmental Protection Agency recommended aquatic bioassay protocols with two standard test organisms-Pimephales promelas and Ceriodaphnia dubia. Results indicated that metals associated with the solid test materials became mobilized in our test system upon interaction with waters of circumneutral pH and reached concentrations sufficient to induce toxicity in both test species. Acute (48 h) LC50 values for P. promelas and C. dubia exposed to leachates prepared from metallofullerene waste solids were 54 and 5% (as % leachate in diluent), respectively. Toxicity was eliminated after adding the chelator EDTA to the leachates, implicating divalent transition metals as the toxicity source. Our results demonstrate the aquatic toxicity of metals mobilized from products and byproducts of nanomanufacturing, and they emphasize the need for a global review of nanomanufacturing wastes and low-purity products.

  15. Sm@C2v(3)-C80: site-hopping motion of endohedral Sm atom and metal-induced effect on redox profile

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Niu, Ben; Shi, Zujin; Lian, Yongfu; Feng, Lai

    2012-10-01

    A new metallofullerene Sm@C2v(3)-C80 was synthesized and characterized. X-Ray analysis showed that the endohedral Sm atom undergoes a hopping motion between several off-center sites, even at low temperature. In addition, a comparative electrochemical study between Sm@C2v(3)-C80 and Yb@C2v(3)-C80 revealed their different redox potentials, suggesting a metal-induced effect on their redox profiles.A new metallofullerene Sm@C2v(3)-C80 was synthesized and characterized. X-Ray analysis showed that the endohedral Sm atom undergoes a hopping motion between several off-center sites, even at low temperature. In addition, a comparative electrochemical study between Sm@C2v(3)-C80 and Yb@C2v(3)-C80 revealed their different redox potentials, suggesting a metal-induced effect on their redox profiles. CCDC reference number 894168. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr32193a

  16. Atomistic simulation of ferroelectric-ferroelastic gadolinium molybdate

    NASA Astrophysics Data System (ADS)

    Dudnikova, V. B.; Zharikov, E. V.

    2017-05-01

    Gadolinium molybdate Gd2(MoO4)3 orthorhombic ferroelectric ferroelastic (β'-phase) is simulated by the method of interatomic potentials. The simulation is performed using the GULP 4.0.1 code (General Utility Lattice Program), which is based on the minimization of the energy of the crystal structure. Parameters of the gadolinium-oxygen interatomic interaction potentials are determined by fitting to the experimental structural data and elastic constants by a procedure available in the GULP code. Atomistic modeling using the effective atomic charges and the system of interatomic potentials made it possible to obtain reasonable estimates of structural parameters, atomic coordinates, and the most important physical, mechanical, and thermodynamic properties of these crystals. Temperature dependences of the heat capacity and vibrational entropy of the crystal are obtained. The calculated parameters of gadolinium-oxygen interaction potentials can be used to simulate more complex gadolinium-containing compounds.

  17. Reply to ``Comment on `Unusual magnetic transitions and nature of magnetic resonance spectra in oxide glasses containing gadolinium' ''

    NASA Astrophysics Data System (ADS)

    Kliava, Janis; Malakhovskii, Alexander; Edelman, Irina; Potseluyko, Anatoly; Melnikova, Svetlana; Petrakovskaja, Eleonora; Zarubina, Tat'Jana; Petrovskii, Gurii; Bruckental, I.; Yeshurun, Y.

    2006-07-01

    In this Reply we show that, contrary to the suggestion of Dubroca, Hack, and Hummel (DHH), the feature observed at ca. 55K in the magnetic susceptibility of gadolinium-containing oxide glasses [as in our earlier paper, Kliava Phys. Rev. B 71, 104406 (2005)] cannot be due to a magnetic transition in oxygen contaminant. In support of this statement, we supply transformed data at low Gd content as well as magnetization curves for a series of glasses containing dysprosium oxide measured with the same superconducting quantum interference device as in our earlier paper. In all these cases the feature in question is absent. Thus, our previous assignment of the 55K feature to a paramagnetic-to-ferromagnetic transition in Gd clusters in the glass remains the only one consistent with the experimental results.

  18. Application of fullerenes in nanomedicine: an update.

    PubMed

    Dellinger, Anthony; Zhou, Zhiguo; Connor, James; Madhankumar, A B; Pamujula, Sarala; Sayes, Christie M; Kepley, Christopher L

    2013-07-01

    Fullerenes are carbon spheres presently being pursued globally for a wide range of applications in nanomedicine. These molecules have unique electronic properties that make them attractive candidates for diagnostic, therapeutic and theranostic applications. Herein, the latest research is discussed on developing fullerene-based therapeutics as antioxidants for inflammatory diseases, their potential as antiviral/bacterial agents, utility as a drug delivery device and the promise of endohedral fullerenes as new MRI contrast agents. The recent discovery that certain fullerene derivatives can stabilize immune effector cells to prevent or inhibit the release of proinflammatory mediators makes them potential candidates for several diseases such as asthma, arthritis and multiple sclerosis. Gadolinium-containing endohedral fullerenes are being pursued as diagnostic MRI contrast agents for several diseases. Finally, a new class of fullerene-based theranostics has been developed, which combine therapeutic and diagnostic capabilities to specifically detect and kill cancer cells.

  19. Acuminated fluorescence of Er3+ centres in endohedral fullerenes through the incarceration of a carbide cluster

    NASA Astrophysics Data System (ADS)

    Plant, Simon R.; Dantelle, Géraldine; Ito, Yasuhiro; Ng, Tsz Cheong; Ardavan, Arzhang; Shinohara, Hisanori; Taylor, Robert A.; Briggs, G. Andrew D.; Porfyrakis, Kyriakos

    2009-07-01

    Photoluminescence spectroscopic measurements have allowed the acquisition of high resolution spectra at low temperature for the endohedral metallofullerenes, Er2 @C82 (isomer I) and Er2C2 @C82 (isomer I). The characteristic emission in the 1.5-1.6 μm region corresponds to the 4I13/2 (m) →4I15/2 (n) transitions of the Er3+ ion for both molecules. The emission arising from Er2C2 @C82 (I) appears acuminated (narrow lines that taper to a point) when compared with that of Er2 @C82 (I) . The Er2C2 @C82 (I) emission linewidths are comparable to those found in crystals, making this molecule of interest for applications where accessible, well-defined quantum states are required.

  20. Recent advances in fullerene science (Invited)

    SciTech Connect

    Dunk, P. W.; Marshall, A. G.; Mulet-Gas, M.; Rodriguez-Fortea, A.; Poblet, J. M.

    2014-12-09

    The development of very high resolution FT-ICR mass spectrometers (Marshall et al, 1998) has made a wide range of new measurements possible and by combining this new technology with laser vaporization supersonic beam methods of producing carbon species (chains, rings and fullerenes), new advances in understanding of the fullerene creation mechanisms and their reactivity have been possible. In this overview, new understanding has been developed with regard to: a) closed-network growth of fullerenes (Dunk et al, 2012a); b) small endohedral species such as MαC{sub 28} (Dunk et al., 2012b); c) metallofullerene and fullerene formation under conditions in stellar outflows with relevance to stardust (Dunk et al., 2013a) and d) The formation of heterofullerenes by direct exposure of C{sub 60} toboron vapor (Dunk et al., 2013b)

  1. Harnessing electron transfer from the perchlorotriphenylmethide anion to Y@C82(C(2v)) to engineer an endometallofullerene-based salt.

    PubMed

    Kareev, Ivan E; Laukhina, Elena; Bubnov, Vyacheslav P; Martynenko, Vyacheslav M; Lloveras, Vega; Vidal-Gancedo, José; Mas-Torrent, Marta; Veciana, Jaume; Rovira, Concepció

    2013-06-03

    We show that electron transfer from the perchlorotriphenylmethide anion (PTM(-)) to Y@C82(C2v) is an instantaneous process, suggesting potential applications for using PTM(-) to perform redox titrations of numerous endohedral metallofullerenes. The first representative of a Y@C82-based salt containing the complex cation was prepared by treating Y@C82(C2v) with the [K(+)([18]crown-6)]PTM(-) salt. The synthesis developed involves the use of the [K(+)([18]crown-6)]PTM(-) salt as a provider of both a complex cation and an electron-donating anion that is able to reduce Y@C82 C2v). For the first time, the molar absorption coefficients for neutral and anionic forms of the pure isomer of Y@C82(C2v) were determined in organic solvents with significantly different polarities. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. In pursuit of nanocarbons.

    PubMed

    Shinohara, Hisanori

    2012-06-01

    With the advent of the Krätschmer-Huffman historical breakthrough on the macroscopic synthesis of C(60) in the late summer of 1990, I decided to stop all my research so far in the area of spectroscopy of gas-phase molecular microclusters. Since then, my odyssey in and quest for the so-called nanocarbons started. Thanks to the brand-new and enchanting world of fullerenes, metallofullerenes, carbon nanotubes and nano-peapods, I have been able to entertain (and still am entertaining!) "the pleasure of finding things out", as Richard Feynman once put it in an interview by a BBC television program in 1981. I believe that as long as one has big dreams and lays the groundwork for the dreams, one will achieve them. My quest for nanocarbons is still on its way. Copyright © 2012 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  3. Synthesis and radiation resistance of fullerenes and fullerene derivatives

    NASA Astrophysics Data System (ADS)

    Shilin, V. A.; Lebedev, V. T.; Sedov, V. P.; Szhogina, A. A.

    2016-07-01

    The parameters of an electric-arc facility for the synthesis of fullerenes and endohedral metallofullerenes are optimized. The resistance of C60 and C70 fullerenes and C60(OH)30 and C70(OH)30 fullerenols against neutron irradiation is studied. It is established that the radiation resistance of the fullerenes is higher than that of the fullerenols, but the radiation resistance of the Gd@C2 n endometallofullerenes is lower than that of the corresponding Gd@C2 n (OH)38 fullerenols. The radiation resistance of mixtures of Me@C2 n (OH)38 ( Me = Gd, Tb, Sc, Fe, and Pr) endometallofullerenes with C60(OH)30 is determined. The factors affecting the radiation resistance of the fullerenes and fullerenols are discussed.

  4. Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage.

    PubMed

    Suenaga, Kazu; Sato, Yuta; Liu, Zheng; Kataura, Hiromichi; Okazaki, Toshiya; Kimoto, Koji; Sawada, Hidetaka; Sasaki, Takeo; Omoto, Kazuya; Tomita, Takeshi; Kaneyama, Toshikatsu; Kondo, Yukihito

    2009-08-01

    Visualizing atoms and discriminating between those of different elements is a goal in many analytical techniques. The use of electron energy-loss spectroscopy (EELS) in such single-atom analyses is hampered by an inherent difficulty related to the damage caused to specimens by incident electrons. Here, we demonstrate the successful EELS single-atom spectroscopy of various metallofullerene-doped single-wall nanotubes (known as peapods) without massive structural destruction. This is achieved by using an incident electron probe with a low accelerating voltage (60 kV). Single calcium atoms inside the peapods were unambiguously identified for the first time using EELS. Elemental analyses of lanthanum, cerium and erbium atoms were also demonstrated, which shows that single atoms with adjacent atomic numbers can be successfully discriminated with this technique.

  5. Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C82 Fullerene Cage: Complete Structural Characterization of Th@C3v(8)-C82.

    PubMed

    Wang, Yaofeng; Morales-Martínez, Roser; Zhang, Xingxing; Yang, Wei; Wang, Yaxing; Rodríguez-Fortea, Antonio; Poblet, Josep M; Feng, Lai; Wang, Shuao; Chen, Ning

    2017-03-31

    Endohedral metallofullerenes (EMFs) containing lanthanides have been intensively studied in recent years. By contrast, actinide endohedral fullerenes remain largely unexplored. Herein, for the first time, we report the single crystal structure and full characterization of an actinide endohedral fullerene, Th@C82, which exhibits remarkably different electronic and spectroscopic properties compared to those of lanthanide EMFs. Single crystal X-ray crystallography unambiguously established the molecular structure as Th@C3v(8)-C82. Combined experimental and theoretical studies reveal that Th@C3v(8)-C82 is the first example of an isolated monometallofullerene with four electrons transferred from the metal to the cage, with a surprisingly large electrochemical band gap of 1.51 eV. Moreover, Th@C3v(8)-C82 displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.

  6. Stability and electronic properties of low-dimensional nanostructures

    NASA Astrophysics Data System (ADS)

    Guan, Jie

    As the devices used in daily life become smaller and more concentrated, traditional three-dimensional (3D) bulk materials have reached their limit in size. Low-dimensional nanomaterials have been attracting more attention in research and getting widely applied in many industrial fields because of their atomic-level size, unique advanced properties, and varied nanostructures. In this thesis, I have studied the stability and mechanical and electronic properties of zero-dimensional (0D) structures including carbon fullerenes, nanotori, metallofullerenes and phosphorus fullerenes, one-dimensional (1D) structures including carbon nanotubes and phosphorus nanotubes, as well as two-dimensional (2D) structures including layered transition metal dichalcogenides (TMDs), phosphorene and phosphorus carbide (PC). I first briefly introduce the scientific background and the motivation of all the work in this thesis. Then the computational techniques, mainly density functional theory (DFT), are reviewed in Chapter 2. In Chapter 3, I investigate the stability and electronic structure of endohedral rare-earth metallofullerene La C60 and the trifluoromethylized La C60(CF3)n with n ≤ 5. Odd n is preferred due to the closed-shell electronic configuration or large HOMO-LUMO gap, which is also meaningful for the separation of C 60-based metallofullerenes. Mechanical and electronic properties of layered materials including TMDs and black phosphorus are studied in Chapter 4 and 5. In Chapter 4, a metallic NbSe2/semiconducting WSe2 bilayer is investigated and besides a rigid band shift associated with charge transfer, the presence of NbSe2 does not modify the electronic structure of WSe2. Structural similarity and small lattice mismatch results in the heterojunction being capable of efficiently transferring charge acrossthe interface. In Chapter 5, I investigate the dependence of stability and electronic band structure on the in-layer strain in bulk black phosphorus. In Chapters 6, 7 and

  7. Physics and Chemistry of Advanced Nanoscale Materials: Experiment, Simulation, and Theory

    NASA Astrophysics Data System (ADS)

    Kiang, Ching-Hwa

    1995-01-01

    This thesis discusses simulation and theory of lattice dynamics as well as experiments on novel forms of carbon. A new crystalline AgBr interaction potential was constructed by fitting literature experimental data. The shell model was successfully used to account for the polarizabilities of the ions. This approach overcame difficulties previous investigators faced in determining the AgBr potential. The very useful shell model was generalized to allow, for the first time, its use in dynamical simulations. The rapid shell dynamics, simulating the electron polarization, were integrated out in a generalized Born-Oppenheimer-like approach. The effective Hamiltonians were derived for both quantum and classical descriptions of the shells. The first crystallization and characterization of a metallofullerene were performed. Endohedral metallofullerenes were synthesized and characterized. Metals such as Sc, Y, and Er that formed stable compounds in fullerene cages were synthesized and products purified. The crystal structure of rm Sc_2C_{84} was determined by transmission electron microscopy study. Experimental studies on fullerenes and related materials lead to the first example of a catalytically -grown, fullerene-like material. We discovered that single -layer carbon nanotubes can be produced by vaporizing cobalt and carbon with an electric arc in a helium atmosphere. Catalyst promoters such as sulfur, bismuth, and lead were found not only to enhance the yield of single-layer nanotubes but also to produce tubes in a diameter range not accessible with cobalt alone. Sulfur, bismuth, and tungsten were found to catalyze the formation of cobalt crystals encapsulated in graphitic polyhedra. Various carbon structures were also produced concurrently, e.g. multilayer nanotubes, strings of carbon nanocompartments, carbon nanofibers, and metal-filled nanomaterials. Nanotubes were observed to undergo real-time structural changes under electron beam heating. A growth model of single

  8. Neutron capture nuclei-containing carbon nanoparticles for destruction of cancer cells.

    PubMed

    Hwang, Kuo Chu; Lai, Po Dong; Chiang, Chi-Shiun; Wang, Pei-Jen; Yuan, Chiun-Jye

    2010-11-01

    HeLa cells were incubated with neutron capture nuclei (boron-10 and gadolinium)-containing carbon nanoparticles, followed by irradiation of slow thermal neutron beam. Under a neutron flux of 6 x 10(11) n/cm(2) (or 10 min irradiation at a neutron flux of 1 x 10(9) n/cm(2) s), the percentages of acute cell death at 8 h after irradiation are 52, 55, and 28% for HeLa cells fed with BCo@CNPs, GdCo@CNPs, and Co@CNPs, respectively. The proliferation capability of the survived HeLa cells was also found to be significantly suppressed. At 48 h after neutron irradiation, the cell viability further decreases to 35 +/- 5% as compared to the control set receiving the same amount of neutron irradiation dose but in the absence of carbon nanoparticles. This work demonstrates "proof-of-concept" examples of neutron capture therapy using (10)B-, (157)Gd-, and (59)Co-containing carbon nanoparticles for effective destruction of cancer cells. It will also be reported the preparation and surface functionalization of boron or gadolinium doped core-shell cobalt/carbon nanoparticles (BCo@CNPs, GdCo@CNPs and Co@CNPs) using a modified DC pulsed arc discharge method, and their characterization by various spectroscopic measurements, including TEM, XRD, SQUID, FT-IR, etc. Tumor cell targeting ability was introduced by surface modification of these carbon nanoparticles with folate moieties.

  9. Aneurysm Sac Pressure Measurement with Minimally Invasive Implantable Pressure Sensors: An Alternative to Current Surveillance Regimes after EVAR?

    SciTech Connect

    Springer, Fabian Guenther, Rolf W.; Schmitz-Rode, Thomas

    2008-05-15

    Current protocols for surveillance after endovascular repair (EVAR) of abdominal aortic aneurysms are mostly based on costly and time-consuming imaging procedures and aim to detect adverse events such as graft migration, endoleaks or aneurysm sac enlargement. These imaging procedures are either associated with radiation exposure to the patients or may be harmful to the patient due to the use of iodine- or gadolinium-containing contrast agents. Furthermore the advantages of EVAR in the short term might be negated by the necessity for endograft surveillance over years. Thus, alternative modalities for follow-up are being investigated. One of these technologies provides pressure information directly from the aneurysm sac. This noninvasive, telemetric pressure sensing was tested in vitro as well as in first clinical trials and was able to identify successful aneurysm exclusion after EVAR. The telemetric pressure sensors showed a promising efficacy and accuracy in detecting type I and type III endoleaks and will help to clarify the clinical relevance of type II endoleaks. This article provides an overview of the in vitro sensors investigated as well as the first clinical trials and the sensors' potential to change the current endograft surveillance regimes.

  10. Specific lipase-responsive polymer-coated gadolinium nanoparticles for MR imaging of early acute pancreatitis.

    PubMed

    Zhang, Hong-Wu; Wang, Li-Qin; Xiang, Qing-Feng; Zhong, Qian; Chen, Lu-Ming; Xu, Cai-Xia; Xiang, Xian-Hong; Xu, Bo; Meng, Fei; Wan, Yi-Qian; Deng, David Y B

    2014-01-01

    Currently, available methods for diagnosis of acute pancreatitis (AP) are mainly dependent on serum enzyme analysis and imaging techniques that are too low in sensitivity and specificity to accurately and promptly diagnose AP. The lack of early diagnostic tools highlights the need to search for a highly effective and specific diagnostic method. In this study, we synthesized a conditionally activated, gadolinium-containing, nanoparticle-based MRI nanoprobe as a diagnostic tool for the early identification of AP. Gadolinium diethylenetriaminepentaacetic fatty acid (Gd-DTPA-FA) nanoparticles were synthesized by conjugation of DTPA-FA ligand and gadolinium acetate. Gd-DTPA-FA exhibited low cytotoxicity and excellent biocompatibility when characterized in vitro and in vivo studies. L-arginine induced a gradual increase in the intensity of the T1-weighted MRI signal from 1 h to 36 h in AP rat models. The increase in signal intensity was most significant at 1 h, 6 h and 12 h. These results suggest that the Gd-DTPA-FA as an MRI contrast agent is highly efficient and specific to detect early AP.

  11. Nuclear design of Helical Cruciform Fuel rods

    SciTech Connect

    Shirvan, K.; Kazimi, M. S.

    2012-07-01

    In order to increase the power density of current and new light water reactor designs, the Helical Cruciform Fuel (HCF) rods are proposed. The HCF rods are equivalent to a cylindrical rod, with the fuel in a cruciform shaped, twisted axially. The HCF rods increase the surface area to volume ratio and inter-subchannel mixing behavior due to their cruciform and helical shapes, respectively. In a previous study, the HCF rods have shown the potential to up-rate existing PWRs by 50% and BWRs by 25%. However, HCF rods do display different neutronics modeling and performance. The cruciform cross section of HCF rods creates radially asymmetric heat generation and temperature distribution. The nominal HCF rod's beginning of life reactivity is reduced, compared to a cylindrical rod with the same fuel volume, by 500 pcm, due to increase in absorption in cladding. The rotation of these rods accounts for reactivity changes, which depends on the H/HM ratio of the pin cell. The HCF geometry shows large sensitivities to U{sup 235} or gadolinium enrichments compared to a cylindrical geometry. In addition, the gadolinium-containing HCF rods show a stronger effect on neighboring HCF rods than in case of cylindrical rods, depending on the orientation of the HCF rods. The helical geometry of the rods introduces axial shadowing of about 600 pcm, not seen in typical cylindrical rods. (authors)

  12. Purification of cerium, neodymium and gadolinium for low background experiments

    NASA Astrophysics Data System (ADS)

    Boiko, R. S.; Barabash, A. S.; Belli, P.; Bernabei, R.; Cappella, F.; Cerulli, R.; Danevich, F. A.; Incicchitti, A.; Laubenstein, M.; Mokina, V. M.; Nisi, S.; Poda, D. V.; Polischuk, O. G.; Tretyak, V. I.

    2014-01-01

    Cerium, neodymium and gadolinium contain double beta active isotopes. The most interesting are 150Nd and 160Gd (promising for 0ν2β search), 136Ce (2β+ candidate with one of the highest Q2β). The main problem of compounds containing lanthanide elements is their high radioactive contamination by uranium, radium, actinium and thorium. The new generation 2β experiments require development of methods for a deep purification of lanthanides from the radioactive elements. A combination of physical and chemical methods was applied to purify cerium, neodymium and gadolinium. Liquid-liquid extraction technique was used to remove traces of Th and U from neodymium, gadolinium and for purification of cerium from Th, U, Ra and K. Co-precipitation and recrystallization methods were utilized for further reduction of the impurities. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe gamma spectrometry. As a result of the purification procedure the radioactive contamination of gadolinium oxide (a similar purification efficiency was reached also with cerium and neodymium oxides) was decreased from 0.12 Bq/kg to 0.007 Bq/kg in 228Th, from 0.04 Bq/kg to <0.006 Bq/kg in 226Ra, and from 0.9 Bq/kg to 0.04 Bq/kg in 40K. The purification methods are much less efficient for chemically very similar radioactive elements like actinium, lanthanum and lutetium.

  13. Localized Corrosion of a Neutron Absorbing Ni-Cr-Mo-Gd Alloy

    SciTech Connect

    R.E. Mizia; T. E. Lister; P. J. Pinhero; T. L. Trowbridge

    2005-04-01

    The National Spent Nuclear Fuel Program, located at the Idaho National Laboratory (INL), has developed a new nickel-chromium-molybdenum-gadolinium structural alloy for storage and long-term disposal of spent nuclear fuel (SNF). The new alloy will be used for SNF storage container inserts for nuclear criticality control. Gadolinium has been chosen as the neutron absorption alloying element due to its high thermal neutron absorption cross section. This alloy must be resistant to localized corrosion when exposed to postulated Yucca Mountain in-package chemistries. The corrosion resistance properties of three experimental heats of this alloy are presented. The alloys performance are be compared to Alloy 22 and borated stainless steel. The results show that initially the new Ni-Cr-Mo-Gd alloy is less resistant to corrosion as compared to another Ni-Cr-Mo-Gd alloy (Alloy 22); but when the secondary phase that contains gadolinium (gadolinide) is dissolved, the alloy surface becomes passive. The focus of this work is to qualify these gadolinium containing materials for ASME code qualification and acceptance in the Yucca Mountain Repository.

  14. Scintillation Counters

    NASA Astrophysics Data System (ADS)

    Bell, Zane W.

    Scintillators find wide use in radiation detection as the detecting medium for gamma/X-rays, and charged and neutral particles. Since the first notice in 1895 by Roentgen of the production of light by X-rays on a barium platinocyanide screen, and Thomas Edison's work over the following 2 years resulting in the discovery of calcium tungstate as a superior fluoroscopy screen, much research and experimentation have been undertaken to discover and elucidate the properties of new scintillators. Scintillators with high density and high atomic number are prized for the detection of gamma rays above 1 MeV; lower atomic number, lower-density materials find use for detecting beta particles and heavy charged particles; hydrogenous scintillators find use in fast-neutron detection; and boron-, lithium-, and gadolinium-containing scintillators are used for slow-neutron detection. This chapter provides the practitioner with an overview of the general characteristics of scintillators, including the variation of probability of interaction with density and atomic number, the characteristics of the light pulse, a list and characteristics of commonly available scintillators and their approximate cost, and recommendations regarding the choice of material for a few specific applications. This chapter does not pretend to present an exhaustive list of scintillators and applications.

  15. Surface interactions with compartmentalized cellular phosphates explain rare earth oxide nanoparticle hazard and provide opportunities for safer design.

    PubMed

    Li, Ruibin; Ji, Zhaoxia; Chang, Chong Hyun; Dunphy, Darren R; Cai, Xiaoming; Meng, Huan; Zhang, Haiyuan; Sun, Bingbing; Wang, Xiang; Dong, Juyao; Lin, Sijie; Wang, Meiying; Liao, Yu-Pei; Brinker, C Jeffrey; Nel, Andre; Xia, Tian

    2014-02-25

    Growing international exploitation of rare earth oxides (REOs) for commercial and biological use has increased the possibility of human exposure and adverse health effects. Occupational exposure to rare earth materials in miners and polishers leads to a severe form of pneumoconiosis, while gadolinium-containing MRI contrast agents cause nephrogenic systemic fibrosis in patients with renal impairment. The mechanisms for inducing these adverse pro-fibrogenic effects are of considerable importance for the safety assessment of REO particles as well as presenting opportunities for safer design. In this study, using a well-prepared REO library, we obtained a mechanistic understanding of how REOs induce cellular and pulmonary damage by a compartmentalized intracellular biotransformation process in lysosomes that results in pro-fibrogenic growth factor production and lung fibrosis. We demonstrate that rare earth oxide ion shedding in acidifying macrophage lysosomes leads to biotic phosphate complexation that results in organelle damage due to stripping of phosphates from the surrounding lipid bilayer. This results in nanoparticle biotransformation into urchin shaped structures and setting in motion a series of events that trigger NLRP3 inflammasome activation, IL-1β release, TGF-β1 and PDGF-AA production. However, pretreatment of REO nanoparticles with phosphate in a neutral pH environment prevents biological transformation and pro-fibrogenic effects. This can be used as a safer design principle for producing rare earth nanoparticles for biological use.

  16. Surface Interactions with Compartmentalized Cellular Phosphates Explain Rare Earth Oxide Nanoparticle Hazard and Provide Opportunities for Safer Design

    PubMed Central

    2014-01-01

    Growing international exploitation of rare earth oxides (REOs) for commercial and biological use has increased the possibility of human exposure and adverse health effects. Occupational exposure to rare earth materials in miners and polishers leads to a severe form of pneumoconiosis, while gadolinium-containing MRI contrast agents cause nephrogenic systemic fibrosis in patients with renal impairment. The mechanisms for inducing these adverse pro-fibrogenic effects are of considerable importance for the safety assessment of REO particles as well as presenting opportunities for safer design. In this study, using a well-prepared REO library, we obtained a mechanistic understanding of how REOs induce cellular and pulmonary damage by a compartmentalized intracellular biotransformation process in lysosomes that results in pro-fibrogenic growth factor production and lung fibrosis. We demonstrate that rare earth oxide ion shedding in acidifying macrophage lysosomes leads to biotic phosphate complexation that results in organelle damage due to stripping of phosphates from the surrounding lipid bilayer. This results in nanoparticle biotransformation into urchin shaped structures and setting in motion a series of events that trigger NLRP3 inflammasome activation, IL-1β release, TGF-β1 and PDGF-AA production. However, pretreatment of REO nanoparticles with phosphate in a neutral pH environment prevents biological transformation and pro-fibrogenic effects. This can be used as a safer design principle for producing rare earth nanoparticles for biological use. PMID:24417322

  17. Crystallographic X-ray analyses of Yb@C(2v)(3)-C80 reveal a feasible rule that governs the location of a rare earth metal inside a medium-sized fullerene.

    PubMed

    Lu, Xing; Lian, Yongfu; Beavers, Christine M; Mizorogi, Naomi; Slanina, Zdenek; Nagase, Shigeru; Akasaka, Takeshi

    2011-07-20

    Single crystal X-ray diffraction studies of Yb@C(2v)(3)-C(80)·Ni(II)(OEP)·CS(2)·1.5C(6)H(6) (OEP = octaethylporphinate) reveal that a relatively flat region of the fullerene interacts with the Ni(II)(OEP) molecule, featuring shape-matching interactions. Surprisingly, it is found that the internal metal is located under a hexagonal carbon ring apart from the 2-fold axis of the C(2v)(3)-C(80) cage, presenting the first example of metallofullerenes with an asymmetrically positioned metal. Such an anomalous location of Yb(2+) is associated with its strong ability to pursue a large coordination number and the lack of hexagon along the C(2) axis of C(2v)(3)-C(80). It is accordingly assumed that a suitable cage hexagon is most likely to be preferred by the single rare earth metal to stay behind inside a medium-sized fullerene, such as C(80) and C(82).

  18. Clusters, Quantum Confinement and Energy Storage

    NASA Astrophysics Data System (ADS)

    Connerade, Jean-Patrick

    One of the challenges posed by the demand for clean urban transportation is the compact and cyclically recoverable storage of energy in quantities sufficient for propulsion. Promising routes, such as the reversible insertion of Li+ ions inside solids for `rocking chair' batteries, require a deformable host material with no irreversibility. Such `soft' deformations are in general highly complex, but the compressibility of atoms or larger systems can be studied directly in situations with simpler symmetry. Thus, the search for `soft' materials leads one to consider certain types of cluster, as well as linear or nearly-spherical structures (chains of metallofullerenes, for example) whose deformations can be computed from the Schrodinger equation. Extended or `giant' atomic models allow one to construct compression-dilation cycles analogous in a rough sense to the Carnot cycle of classical thermodynamics. This simplified approach suggests that, even for idealised systems, there are constraints on the reversible storage and recovery of energy, and that (when applied to realistic structures) modelling based on such principles might help in the selection of appropriate materials.

  19. Crystallographic Evidence for Direct Metal-Metal Bonding in a Stable Open-Shell La2 @Ih -C80 Derivative.

    PubMed

    Bao, Lipiao; Chen, Muqing; Pan, Changwang; Yamaguchi, Takahisa; Kato, Tatsuhisa; Olmstead, Marilyn M; Balch, Alan L; Akasaka, Takeshi; Lu, Xing

    2016-03-18

    Endohedral metallofullerenes (EMFs) have novel structures and properties that are closely associated with the internal metallic species. Benzyl radical additions have been previously shown to form closed-shell adducts by attaching an odd number of addends to open-shell EMFs (such as Sc3 C2 @Ih -C80 ) whereas an even number of groups are added to closed-shell EMFs (for example Sc3 N@Ih -C80 ). Herein we report that benzyl radical addition to the closed-shell La2 @Ih -C80 forms a stable, open-shell monoadduct instead of the anticipated closed-shell bisadduct. Single-crystal X-ray diffraction results show the formation of a stable radical species. In this species, the La-La distance is comparable to the theoretical value of a La-La covalent bond and is shorter than reported values for other La2 @Ih -C80 derivatives, providing unambiguous evidence for the formation of direct La-La bond.

  20. From Pauli's birthday to 'Confinement Resonances' - a potted history of Quantum Confinement

    NASA Astrophysics Data System (ADS)

    Connerade, J. P.

    2013-06-01

    Quantum Confinement is in some sense a new subject. International meetings dedicated to Quantum Confinement have occurred only recently in Mexico City (the first in 2010 and the second, in September 2011). However, at least in principle, the subject has existed since a very long time. Surprisingly perhaps, it lay dormant for many years, for want of suitable experimental examples. However, when one looks carefully at its origin, it turns out to have a long and distinguished history. In fact, the problem of quantum confinement raises a number of very interesting issues concerning boundary conditions in elementary quantum mechanics and how they should be applied to real problems. Some of these issues were missed in the earliest papers, but are implicit in the structure of quantum mechanics, and lead to the notion of Confinement Resonances, the existence of which was predicted theoretically more than ten years ago. Although, for several reasons, these resonances remained elusive for a very long time, they have now been observed experimentally, which puts the whole subject in much better shape and, together with the advent of metallofullerenes, has contributed to its revival.

  1. Biosafety assessment of Gd@C82(OH)22 nanoparticles on Caenorhabditis elegans

    NASA Astrophysics Data System (ADS)

    Zhang, Wendi; Sun, Baoyun; Zhang, Longze; Zhao, Baolu; Nie, Guangjun; Zhao, Yuliang

    2011-06-01

    Gd@C82(OH)22, a water-soluble endohedral metallofullerene derivative, has been proven to possess significant antineoplastic activity in mice. Toxicity studies of the nanoparticle have shown some evidence of low or non toxicity in mice and cell models. Here we employed Caenorhabditis elegans (C. elegans) as a model organism to further evaluate the short- and long-term toxicity of Gd@C82(OH)22 and possible behavior changes under normal and stress culture conditions. With treatment of Gd@C82(OH)22 at 0.01, 0.1, 1.0 and 10 μg ml-1 within one generation (short-term), C. elegans showed no significant decrease in longevity or thermotolerance compared to the controls. Furthermore, when Gd@C82(OH)22 treatment was extended up to six generations (long-term), non-toxic effects to the nematodes were found. In addition, data from body length measurement, feeding rate and egg-laying assays with short-term treatment demonstrated that the nanoparticles have no significant impact on the individual growth, feeding behavior and reproductive ability, respectively. In summary, this work has shown that Gd@C82(OH)22 is tolerated well by worms and it has no apparent toxic effects on longevity, stress resistance, growth and behaviors that were observed in both adult and young worms. Our work lays the foundations for further developments of this anti-neoplastic agent for clinical applications.

  2. Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene

    NASA Astrophysics Data System (ADS)

    Liu, Fupin; Krylov, Denis S.; Spree, Lukas; Avdoshenko, Stanislav M.; Samoylova, Nataliya A.; Rosenkranz, Marco; Kostanyan, Aram; Greber, Thomas; Wolter, Anja U. B.; Büchner, Bernd; Popov, Alexey A.

    2017-07-01

    Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μB with a dysprosium-electron exchange constant of 32 cm-1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.

  3. Structural Stability and Deformation of Solvated Sm@C2(45)-C90 under High Pressure

    PubMed Central

    Cui, Jinxing; Yao, Mingguang; Yang, Hua; Liu, Ziyang; Liu, Shijie; Du, Mingrun; Li, Quanjun; Liu, Ran; Cui, Tian; Liu, Bingbing

    2016-01-01

    Solvated fullerenes recently have been shown to exhibit novel compression behaviors compared with the pristine fullerenes. However, less attention has been focused on the large cage endohedral metallofullerenes. Here, we have firstly synthesized solvated Sm@C90 microrods by a solution drop-drying method, and then studied the transformations under high pressure. The pressure-induced structural evolutions of Sm@C90 molecules both undergo deformation and collapse. The band gaps of both samples decrease with increasing pressure. The trapped Sm atom plays a role in restraining the compression of the adjacent bonds. The solvent plays a role in protecting Sm@C90 against collapse in the region of 12–20 GPa, decreasing and postponing the change of band gap. Above 30 GPa, the carbon cages collapse. Released from 45 GPa, the compressed solvated Sm@C90 forms a new ordered amorphous carbon cluster (OACC) structure with metal atoms trapped in the units of amorphous carbon clusters, which is different from the OACC structure formed by compressing solvated C60 and C70. This discovery opens the door for the creation of new carbon materials with desirable structural and physical properties when suitable starting materials are selected. PMID:27503144

  4. Structural Stability and Deformation of Solvated Sm@C2(45)-C90 under High Pressure.

    PubMed

    Cui, Jinxing; Yao, Mingguang; Yang, Hua; Liu, Ziyang; Liu, Shijie; Du, Mingrun; Li, Quanjun; Liu, Ran; Cui, Tian; Liu, Bingbing

    2016-08-09

    Solvated fullerenes recently have been shown to exhibit novel compression behaviors compared with the pristine fullerenes. However, less attention has been focused on the large cage endohedral metallofullerenes. Here, we have firstly synthesized solvated Sm@C90 microrods by a solution drop-drying method, and then studied the transformations under high pressure. The pressure-induced structural evolutions of Sm@C90 molecules both undergo deformation and collapse. The band gaps of both samples decrease with increasing pressure. The trapped Sm atom plays a role in restraining the compression of the adjacent bonds. The solvent plays a role in protecting Sm@C90 against collapse in the region of 12-20 GPa, decreasing and postponing the change of band gap. Above 30 GPa, the carbon cages collapse. Released from 45 GPa, the compressed solvated Sm@C90 forms a new ordered amorphous carbon cluster (OACC) structure with metal atoms trapped in the units of amorphous carbon clusters, which is different from the OACC structure formed by compressing solvated C60 and C70. This discovery opens the door for the creation of new carbon materials with desirable structural and physical properties when suitable starting materials are selected.

  5. The ground state and electronic structure of Gd@C{sub 82}: A systematic theoretical investigation of first principle density functionals

    SciTech Connect

    Dai, Xing; Gao, Yang; Xin, Minsi; Wang, Zhigang; Zhou, Ruhong

    2014-12-28

    As a representative lanthanide endohedral metallofullerene, Gd@C{sub 82} has attracted a widespread attention among theorists and experimentalists ever since its first synthesis. Through comprehensive comparisons and discussions, as well as references to the latest high precision experiments, we evaluated the performance of different computational methods. Our results showed that the appropriate choice of the exchange-correlation functionals is the decisive factor to accurately predict both geometric and electronic structures for Gd@C{sub 82}. The electronic structure of the ground state and energy gap between the septet ground state and the nonet low-lying state obtained from pure density functional methods, such as PBE and PW91, are in good agreement with current experiment. Unlike pure functionals, the popularly used hybrid functionals in previous studies, such as B3LYP, could infer the qualitative correct ground state only when small basis set for C atoms is employed. Furthermore, we also highlighted that other geometric structures of Gd@C{sub 82} with the Gd staying at different positions are either not stable or with higher energies. This work should provide some useful references for various theoretical methodologies in further density functional studies on Gd@C{sub 82} and its derivatives in the future.

  6. Extractions of Y@C{sub 60}, Ba@C{sub 60}, La@C{sub 60}, Ce@C{sub 60}, Pr@C{sub 60}, Nd@C{sub 60}, and Gd@C{sub 60} with aniline

    SciTech Connect

    Kubozono, Yoshihiro; Maeda, Hironobu; Takabayashi, Yasuhiro; Hiraoka, Koji; Nakai, Takeshi; Kashino, Setsuo; Emura, Shuichi; Ukita, Shigeyuki; Sogabe, Toshiaki

    1996-07-24

    Recently many endohedral metallofullerenes such as M@C{sub 74}, M@C{sub 80}, and M@C{sub 82} (M: metal atom) have been successfully isolated by the high performance liquid chromatography (HPLC) technique. Some M@C{sub 60} were prepared in primary soots by an arc-heating or a laser-vaporization method, but the isolation of M@C{sub 60} has not yet been achieved because of the difficulties in extraction; only the extraction of Ca@C{sub 60} with pyridine has been reported as for. Recently we found that aniline is a suitable extraction solvent for Ca@C{sub 60} and Sr@C{sub 60}. For the isolation of M@C{sub 60} by an HPLC technique it is important to find a suitable extraction solvent for M@C{sub 60}. In the present study, we report the successful extraction of Y@C{sub 60}, Ba@C{sub 60}, La@C{sub 60}, Ce@C{sub 60}, Pr@C{sub 60}, Nd@C{sub 60}, and Gd@C{sub 60} with aniline under an air atmosphere. 14 refs., 2 figs.

  7. Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene

    PubMed Central

    Liu, Fupin; Krylov, Denis S.; Spree, Lukas; Avdoshenko, Stanislav M.; Samoylova, Nataliya A.; Rosenkranz, Marco; Kostanyan, Aram; Greber, Thomas; Wolter, Anja U. B.; Büchner, Bernd; Popov, Alexey A.

    2017-01-01

    Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μB with a dysprosium-electron exchange constant of 32 cm−1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped. PMID:28706223

  8. Impacts of fullerene derivatives on regulating the structure and assembly of collagen molecules.

    PubMed

    Yin, Xiaohui; Zhao, Lina; Kang, Seung-gu; Pan, Jun; Song, Yan; Zhang, Mingyi; Xing, Gengmei; Wang, Fei; Li, Jingyuan; Zhou, Ruhong; Zhao, Yuliang

    2013-08-21

    During cancer development, the fibrous layers surrounding the tumor surface get thin and stiff which facilitates the tumor metastasis. After the treatment of metallofullerene derivatives Gd@C82(OH)22, the fibrous layers become thicker and softer, the metastasis of tumor is then largely suppressed. The effect of Gd@C82(OH)22 was found to be related to their direct interaction with collagen and the resulting impact on the structure of collagen fibrils, the major component of extracellular matrices. In this work we study the interaction of Gd@C82(OH)22 with collagen by molecular dynamics simulations. We find that Gd@C82(OH)22 can enhance the rigidity of the native structure of collagen molecules and promote the formation of an oligomer or a microfibril. The interaction with Gd@C82(OH)22 may regulate further the assembly of collagen fibrils and change the biophysical properties of collagen. The control run with fullerene derivatives C60(OH)24 also indicates that C60(OH)24 can influence the structure and assembly of collagen molecules as well, but to a lesser degree. Both fullerene derivatives can form hydrogen bonds with multiple collagen molecules acting as a "fullerenol-mediated bridge" that enhance the interaction within or among collagen molecules. Compared to C60(OH)24, the interaction of Gd@C82(OH)22 with collagen is stronger, resulting in particular biomedical effects for regulating the biophysical properties of collagen fibrils.

  9. Synthesis and electrochemical studies of Bingel-Hirsch derivatives of M(3)N@I(h)-C(80) (M=Sc, Lu).

    PubMed

    Pinzón, Julio R; Zuo, Tianming; Echegoyen, Luis

    2010-04-26

    Bingel-Hirsch derivatives of the trimetallic nitride template endohedral metallofullerenes (TNT-EMFs) Sc(3)N@I(h)-C(80) and Lu(3)N@I(h)-C(80) were prepared by reacting these compounds with 2-bromodiethyl malonate, 2-bromo-1,3-dipyrrolidin-1-ylpropane-1,3-dionate bromide, and 9-bromo fluorene. The mono-adducts were isolated and their (1)H NMR spectra showed that the addition occurred with high regioselectivity at the [6,6] bonds of the I(h)-C(80) fullerene cage. Electrochemical analysis showed that the reductive electrochemistry behavior of these derivatives is irreversible at a scan rate of 100 mV s(-1), which is comparable to the behavior of the pristine fullerene species. The first reduction potential of each derivative is either cathodically or anodically shifted by a different value, depending on the attached addend. Bis-adducts containing EtOOC-C-COOEt and HC-COOEt addends were isolated by HPLC and in the case of Sc(3)N@I(h)-C(80) the first reduction potential exhibits a larger shift towards negative potentials when compared to the mono-adduct. This observation is important for designing acceptor materials for the construction of bulk heterojunction (BHJ) organic solar cells, since the polyfunctionalization not only increases the solubility of the fullerene species but also offers a promising approach for bringing the LUMO energy levels closer for the donor and the acceptor materials.

  10. Lu2@C2n (2n = 82, 84, 86): Crystallographic Evidence of Direct Lu-Lu Bonding between Two Divalent Lutetium Ions Inside Fullerene Cages.

    PubMed

    Shen, Wangqiang; Bao, Lipiao; Wu, Yongbo; Pan, Changwang; Zhao, Shasha; Fang, Hongyun; Xie, Yunpeng; Jin, Peng; Peng, Ping; Li, Fang-Fang; Lu, Xing

    2017-07-26

    Although most of the M2C2n-type metallofullerenes (EMFs) tend to form carbide cluster EMFs, we report herein that Lu-containing EMFs Lu2C2n (2n = 82, 84, 86) are actually dimetallofullerenes (di-EMFs), namely, Lu2@Cs(6)-C82, Lu2@C3v(8)-C82, Lu2@D2d(23)-C84, and Lu2@C2v(9)-C86. Unambiguous X-ray results demonstrate the formation of a Lu-Lu single bond between two lutetium ions which transfers four electrons in total to the fullerene cages, thus resulting in a formal divalent state for each Lu ion. Population analysis indicates that each Lu atom formally donates a 5d electron and a 6s electron to the cage with the remaining 6s electron shared with the other Lu atom to form a Lu-Lu single bond so that only four electrons are transferred to the fullerene cages with the formal divalent valence for each lutetium ion. Accordingly, we confirmed both experimentally and theoretically that the dominating formation of di-EMFs is thermodynamically very favorable for Lu2C2n isomers.

  11. Theoretical survey on M@C80 (M = Ca, Sr, and Ba): Behavior of different alkaline earth metal impacting the chemical stability and electronic properties

    NASA Astrophysics Data System (ADS)

    Cui, Jin-Bo; Guo, Yi-Jun; Li, Qiao-Zhi; Zhao, Pei; Zhao, Xiang

    2016-08-01

    Structures of mono-metallofullerenes M@C80 (M = Ca, Sr, and Ba) that separated in early experiment are determined owning the C2v(31920)-C80 cage. The change rule of properties for M@C80 (M = Ca, Sr, and Ba) influenced by different inner metal are discussed. As the trapped metal changes from calcium to barium, performance of thermodynamic stabilities for M@C2v(31920)-C80, M@C2v(31922)-C80, and M@D5h(31923)-C80 are significantly different. Orbital analysis suggests that the lowest unoccupied molecular orbitals (LUMOs) of Ca@C2v(31920)-C80 and Ca@D5h(31923)-C80 are mostly located on the trapped metal, whereas reduction reactions of Ca@C2v(31920)-C80 and Ca@D5h(31923)-C80 occur on the fullerene cage. Natural electron configuration analyses demonstrates that the decentralized electron back-donation of Ba@C2v(31920)-C80 would take responsible for the instability of itself. Electronic properties such as electron affinities and ionization potentials are significantly affected by encapsulated metal are also found. Computational UV-visible-NIR spectra for M@C2v(31920)-C80 (M = Ca, Sr, Ba) are in perfect accord with the spectra obtained experimentally.

  12. A new contrast media for functional MR urography: Gd-MAG3.

    PubMed

    Algin, Oktay

    2011-07-01

    Tc-99m-MAG3 (tubular agent) provides high imaging quality and extraction efficiency; and has become one of the most widely used agent for scintigraphic examinations of urinary system pathologies and renal transplants. Recently, it was reported that functional magnetic resonance urography (FMRU) can be sufficient in detection of urinary tract obstruction, renal artery stenosis, calculation of kidney functions and evaluation of renal transplants. However the pharmacokinetics of magnetic resonance (MR) contrast-media used in FMRU and Tc-99m-MAG3 differs from each other. This may cause discordant results between the FMRU and most of the scintigraphic studies. To our knowledge, there is no contrast-media which is specific for FMRU. A kidney specific contrast material can be developed for FMRU studies as well. MAG3 is a good candidate for this chelation. In conclusion, MR imaging (MRI) will be the most useful and important technique for morphologic-functional evaluation of urinary system. FMRU examinations performed with MAG3 chelated gadolinium can be sufficient for the complete evaluation of urinary tract even in patients with impaired renal functions ("all in one MRI"). MRI has some important advantages including no risk for radiation exposure, high temporal and spatial resolution, no need for nephrotoxic contrast agent; besides being a fast and feasible technique. Gadolinium-containing contrast agents may cause a life-threatening adverse reaction known as nephrogenic systemic fibrosis in patients with severe renal impairment, but Gd-MAG3 may reduce the risk of nephrogenic systemic fibrosis due to its higher extraction capacity and other features.

  13. Quantitative Molecular Imaging with a Single Gd-Based Contrast Agent Reveals Specific Tumor Binding and Retention in Vivo.

    PubMed

    Johansen, Mette L; Gao, Ying; Hutnick, Melanie A; Craig, Sonya E L; Pokorski, Jonathan K; Flask, Chris A; Brady-Kalnay, Susann M

    2017-06-06

    Magnetic resonance imaging (MRI) has become an indispensable tool in the diagnosis and treatment of many diseases, especially cancer. However, the poor sensitivity of MRI relative to other imaging modalities, such as PET, has hindered the development and clinical use of molecular MRI contrast agents that could provide vital diagnostic information by specifically locating a molecular target altered in the disease process. This work describes the specific and sustained in vivo binding and retention of a protein tyrosine phosphatase mu (PTPμ)-targeted, molecular magnetic resonance (MR) contrast agent with a single gadolinium (Gd) chelate using a quantitative MRI T1 mapping technique in glioma xenografts. Quantitative T1 mapping is an imaging method used to measure the longitudinal relaxation time, the T1 relaxation time, of protons in a magnetic field after excitation by a radiofrequency pulse. T1 relaxation times can in turn be used to calculate the concentration of a gadolinium-containing contrast agent in a region of interest, thereby allowing the retention or clearance of an agent to be quantified. In this context, retention is a measure of molecular contrast agent binding. Using conventional peptide chemistry, a PTPμ-targeted peptide was linked to a chelator that had been conjugated to a lysine residue. Following complexation with Gd, this PTPμ-targeted molecular contrast agent containing a single Gd ion showed significant tumor enhancement and a sustained increase in Gd concentration in both heterotopic and orthotopic tumors using dynamic quantitative MRI. This single Gd-containing PTPμ agent was more effective than our previous version with three Gd ions. Differences between nonspecific and specific agents, due to specific tumor binding, can be determined within the first 30 min after agent administration by examining clearance rates. This more facile chemistry, when combined with quantitative MR techniques, allows for widespread adoption by academic and

  14. Magnetic resonance imaging tracking and assessing repair function of the bone marrow mesenchymal stem cells transplantation in a rat model of spinal cord injury.

    PubMed

    Zhang, Hongwu; Wang, Liqin; Wen, Shihong; Xiang, Qingfeng; Xiang, Xianhong; Xu, Caixia; Wan, Yong; Wang, Jingnan; Li, Bin; Wan, Yiqian; Yang, Zhiyun; Deng, David Y B

    2017-08-29

    The transplantation of bone marrow mesenchymal stem cells (BMSCs) to repair spinal cord injury (SCI) has become a promising therapy. However, there is still a lack of visual evidence directly implicating the transplanted cells as the source of the improvement of spinal cord function. In this study, BMSCs were labeled with NF-200 promoter and lipase-activated gadolinium-containing nanoparticles (Gd-DTPA-FA). Double labeled BMSCs were implanted into spinal cord transaction injury in rat models in situ, the function recovery was evaluated on 1st, 7th, 14th, 28 th days by MRI, Diffusion Tensor Imaing, CT imaging and post-processing, and histological observations. BBB scores were used for assessing function recovery. After transplantation of BMSCs, the hypersignal emerged in spinal cord in T1WI starting at day 7 that was focused at the injection site, which then increased and extended until day 14. Subsequently, the increased signal intensity area rapidly spread from the injection site to entire injured segment lasting four weeks. The diffusion tensor tractography and histological analysis both showed the nerve fibre from dividing to connecting partly. Immunofluorescence showed higher expression of NF-200 in Repaired group than Injury group. Electron microscopy showed detachment and loose of myelin lamellar getting better in Repaired group compared with the Injury group. BBB scores in Repaired group were significantly higher than those of injury animals. Our study suggests that the migration and distribution of Gd-DTPA-FA labeled BMSCs can be tracked using MRI. Transplantation of BMSCs represents a promising potential strategy for the repair of SCI.

  15. Gadolinium accumulation in organs of Sprague-Dawley® rats after implantation of a biodegradable magnesium-gadolinium alloy.

    PubMed

    Myrissa, Anastasia; Braeuer, Simone; Martinelli, Elisabeth; Willumeit-Römer, Regine; Goessler, Walter; Weinberg, Annelie Martina

    2017-01-15

    Biodegradable magnesium implants are under investigation because of their promising properties as medical devices. For enhancing the mechanical properties and the degradation resistance, rare earth elements are often used as alloying elements. In this study Mg10Gd pins were implanted into Sprague-Dawley® rats. The pin volume loss and a possible accumulation of magnesium and gadolinium in the rats' organs and blood were investigated in a long-term study over 36weeks. The results showed that Mg10Gd is a fast disintegrating material. Already 12weeks after implantation the alloy is fragmented to smaller particles, which can be found within the intramedullary cavity and the cortical bones. They disturbed the bone remodeling until the end of the study. The results concerning the elements' distribution in the animals' bodies were even more striking, since an accumulation of gadolinium could be observed in the investigated organs over the whole time span. The most affected tissue was the spleen, with up to 3240μgGd/kg wet mass, followed by the lung, liver and kidney (up to 1040, 685 and 207μgGd/kg). In the brain, muscle and heart, the gadolinium concentrations were much smaller (less than 20μg/kg), but an accumulation could still be detected. Interestingly, blood serum samples showed no accumulation of magnesium and gadolinium. This is the first time that an accumulation of gadolinium in animal organs was observed after the application of a gadolinium-containing degradable magnesium implant. These findings demonstrate the importance of future investigations concerning the distribution of the constituents of new biodegradable materials in the body, to ensure the patients' safety.

  16. Analysis and Speciation of Lanthanoides by ICP-MS

    NASA Astrophysics Data System (ADS)

    Telgmann, Lena; Lindner, Uwe; Lingott, Jana; Jakubowski, Norbert

    2016-11-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is based on formation of positively charged atomic ions in a high-frequency inductively coupled Argon plasma at atmospheric pressure. The ions are extracted and transferred from the plasma source into a mass analyzer operated at high vacuum via an interface equipped with a sampling and a skimmer cone. The ions are separated in the mass analyzer according to their charge to mass ratio. The ions are converted at a conversion dynode and are detected by use of a secondary electron multiplier or a Faraday cup. From an analytical point of view, ICP-MS is a well-established method for multi-elemental analysis in particular for elements at trace- and ultra-trace levels. Furthermore, methods based on ICP-MS offer simple quantification concepts, for which usually (liquid) standards are applied, low matrix effects compared to other conventional analytical techniques, and relative limits of detection (LODs) in the low pg g-1 range and absolute LODs down to the attomol range. For these applications, ICP-MS excels by a high sensitivity which is independent of the molecular structure and a wide linear dynamic range. It has found acceptance in various application areas and during the last decade ICP-MS is also more and more applied for detection of rare earth elements particularly in the life sciences. Due to the fact that all molecules introduced into the high temperature of the plasma in the ion source were completely dissociated and broken down into atoms, which are subsequently ionized, all elemental species information is completely lost. However, if the different species are separated before they enter the plasma by using adequate fractionation or separation techniques, then ICP-MS can be used as a very sensitive element-specific detector. We will discuss this feature of ICP-MS in this chapter in more detail at hand of the speciation of gadolinium-containing contrast agents.

  17. Impacts of fullerene derivatives on regulating the structure and assembly of collagen molecules

    NASA Astrophysics Data System (ADS)

    Yin, Xiaohui; Zhao, Lina; Kang, Seung-Gu; Pan, Jun; Song, Yan; Zhang, Mingyi; Xing, Gengmei; Wang, Fei; Li, Jingyuan; Zhou, Ruhong; Zhao, Yuliang

    2013-07-01

    During cancer development, the fibrous layers surrounding the tumor surface get thin and stiff which facilitates the tumor metastasis. After the treatment of metallofullerene derivatives Gd@C82(OH)22, the fibrous layers become thicker and softer, the metastasis of tumor is then largely suppressed. The effect of Gd@C82(OH)22 was found to be related to their direct interaction with collagen and the resulting impact on the structure of collagen fibrils, the major component of extracellular matrices. In this work we study the interaction of Gd@C82(OH)22 with collagen by molecular dynamics simulations. We find that Gd@C82(OH)22 can enhance the rigidity of the native structure of collagen molecules and promote the formation of an oligomer or a microfibril. The interaction with Gd@C82(OH)22 may regulate further the assembly of collagen fibrils and change the biophysical properties of collagen. The control run with fullerene derivatives C60(OH)24 also indicates that C60(OH)24 can influence the structure and assembly of collagen molecules as well, but to a lesser degree. Both fullerene derivatives can form hydrogen bonds with multiple collagen molecules acting as a ``fullerenol-mediated bridge'' that enhance the interaction within or among collagen molecules. Compared to C60(OH)24, the interaction of Gd@C82(OH)22 with collagen is stronger, resulting in particular biomedical effects for regulating the biophysical properties of collagen fibrils.During cancer development, the fibrous layers surrounding the tumor surface get thin and stiff which facilitates the tumor metastasis. After the treatment of metallofullerene derivatives Gd@C82(OH)22, the fibrous layers become thicker and softer, the metastasis of tumor is then largely suppressed. The effect of Gd@C82(OH)22 was found to be related to their direct interaction with collagen and the resulting impact on the structure of collagen fibrils, the major component of extracellular matrices. In this work we study the interaction

  18. Endohedral metal or a fullerene cage based oxidation? Redox duality of nitride clusterfullerenes Ce(x)M(3-x)N@C(78-88) (x = 1, 2; M = Sc and Y) dictated by the encaged metals and the carbon cage size.

    PubMed

    Zhang, Yang; Popov, Alexey A; Dunsch, Lothar

    2014-01-21

    Redox behavior of endohedral metallofullerenes, in particular their oxidation process, can be classified as a fullerene-based or endohedral species-based process according to the mechanism of the electron transfer. Here we report on the phenomenon of the strain-driven electrochemical behavior achieved by encapsulating the cerium-containing clusters into a series of carbon cages ranging from C78 to C88. The Ce-based mixed metal nitride clusterfullerenes CexM3-xN@C2n (x = 1, 2; M = Sc or Y; 2n = 78-88) were synthesized and characterized. The magnitude of the inherent strain caused by the limited inner space of the carbon cage for the relatively large nitride clusters can be varied by choosing different scaffold metals (Sc, Lu, or Y) to tailor the size of the encaged CexM3-xN cluster and by matching the nitride cluster with different fullerene cages in the size range from C78 to C88. The redox properties of CexM3-xN@C2n were investigated by cyclic and square wave voltammetry. The mechanism of the electrochemical oxidation of Ce-based mixed metal nitride clusterfullerenes, in particular whether the fullerene-based oxidation or the Ce(III) → Ce(IV) process is observed, is found to be dependent on the scaffold metal and the size of the fullerene cage. The endohedral oxidation of Ce(III) to Ce(IV) was observed for a number of compounds as revealed by the negative shift of their oxidation potentials with respect to the values measured for the non-Ce analogues. Experimental studies are supported by DFT calculations. We conclude that the prerequisites for the Ce-based endohedral oxidation process are suitable inherent cluster-cage strain and sufficiently high oxidation potential of the fullerene cage.

  19. Production of Endohedral Fullerenes by Ion Implantation

    SciTech Connect

    Diener, M.D.; Alford, J. M.; Mirzadeh, S.

    2007-05-31

    The empty interior cavity of fullerenes has long been touted for containment of radionuclides during in vivo transport, during radioimmunotherapy (RIT) and radioimaging for example. As the chemistry required to open a hole in fullerene is complex and exceedingly unlikely to occur in vivo, and conformational stability of the fullerene cage is absolute, atoms trapped within fullerenes can only be released during extremely energetic events. Encapsulating radionuclides in fullerenes could therefore potentially eliminate undesired toxicity resulting from leakage and catabolism of radionuclides administered with other techniques. At the start of this project however, methods for production of transition metal and p-electron metal endohedral fullerenes were completely unknown, and only one method for production of endohedral radiofullerenes was known. They therefore investigated three different methods for the production of therapeutically useful endohedral metallofullerenes: (1) implantation of ions using the high intensity ion beam at the Oak Ridge National Laboratory (ORNL) Surface Modification and Characterization Research Center (SMAC) and fullerenes as the target; (2) implantation of ions using the recoil energy following alpha decay; and (3) implantation of ions using the recoil energy following neutron capture, using ORNL's High Flux Isotope Reactor (HFIR) as a thermal neutron source. While they were unable to obtain evidence of successful implantation using the ion beam at SMAC, recoil following alpha decay and neutron capture were both found to be economically viable methods for the production of therapeutically useful radiofullerenes. In this report, the procedures for preparing fullerenes containing the isotopes {sup 212}Pb, {sup 212}Bi, {sup 213}Bi, and {sup 177}Lu are described. None of these endohedral fullerenes had ever previously been prepared, and all of these radioisotopes are actively under investigation for RIT. Additionally, the chemistry for

  20. Technegas: A medical application of {sup 99m}Tc for the study of buckyballs, blood clots, lung disease and AIDS

    SciTech Connect

    Willett, G.D.; Dance, I.G.; Fisher, K.J.; Burch, W.M.; Dasaklis, C.; Mackey, D.W.J.

    1994-12-31

    Radionuclide studies of lung disease have been greatly enhanced by the introduction of an Australian invention; the Technegas generator. The properties of the {open_quotes}dry radio-aerosols{close_quotes} produced by this device ensure lung images superior to those from true radio-gases such as {sup 133}Xe with the additional advantage of employing {sup 99m}Tc, the most widespread radionuclide agent. A Technegas lung scan can enable identification of pulmonary mebolism (an immediately life threatening condition) emphysema and chronic obstructive lung disease. A simple modification to the generator gas mixture produces Pertechnegas an agent useful in studies of the integrity of the alveolar epithelial membrane in immunosuppressed patients such as transplants and AIDS. Although these agents are now common in Australia and Europe, little has been proven of their chemical composites. Technegas is formed by the initial evaporation of ({sup 99m}Tc) sodium pertechnetate with the subsequent sublimation of carbon from a disposable graphite crucible at {approximately}2500{degrees}C in an atmosphere of 100% argon. {sup 99m}Tc atoms are lifted off with the crystalline layers of graphite during the vaporization. Technegas then possibly consists of {sup 99m}Tc based metallo-fullerenes and fullerenes. Technegas has an effective half life in the lung very similar to the physical half life of Technetium (6 hours) regardless of clinical condition; a result which suggests that Technegas contains endohedral fullerenes. Pertechnegas is created in an atmosphere of 97% Ar 3% O{sub 2} and has an effective half life in the lung of less than 15 minutes.

  1. Synthesis and Isolation of the Titanium–Scandium Endohedral Fullerenes—Sc2TiC@Ih-C80, Sc2TiC@D5h-C80 and Sc2TiC2@Ih-C80 : Metal Size Tuning of the TiIV/TiIII Redox Potentials

    PubMed Central

    Junghans, Katrin; Ghiassi, Kamran B.; Samoylova, Nataliya A.; Deng, Qingming; Rosenkranz, Marco; Olmstead, Marilyn M.; Balch, Alan L.; Popov, Alexey A.

    2016-01-01

    The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed-metal Sc–Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4C2@C80 (the most abundant EMF from this synthesis), Sc3C2@C80, isomers of Sc2C2@C82, and the family Sc2C2n (2n=74, 76, 82, 86, 90, etc.), as well as Sc3CH@C80. The Sc–Ti/CH4 system produces the mixed-metal Sc2TiC@C2n (2n=68, 78, 80) and Sc2TiC2@C2n (2n=80) clusterfullerene families. The molecular structures of the new, transition-metal-containing endohedral fullerenes, Sc2TiC@Ih-C80, Sc2TiC@D5h-C80, and Sc2TiC2@Ih-C80, were characterized by NMR spectroscopy. The structure of Sc2TiC@Ih-C80 was also determined by single-crystal X-ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2TiC- and Sc2TiC2-containing clusterfullerenes have Ti-localized LUMOs. Encapsulation of the redox-active Ti ion inside the fullerene cage enables analysis of the cluster–cage strain in the endohedral fullerenes through electrochemical measurements. PMID:27459520

  2. Synthesis and Isolation of the Titanium-Scandium Endohedral Fullerenes-Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 and Sc2 TiC2 @Ih -C80 : Metal Size Tuning of the Ti(IV) /Ti(III) Redox Potentials.

    PubMed

    Junghans, Katrin; Ghiassi, Kamran B; Samoylova, Nataliya A; Deng, Qingming; Rosenkranz, Marco; Olmstead, Marilyn M; Balch, Alan L; Popov, Alexey A

    2016-09-05

    The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed-metal Sc-Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4 C2 @C80 (the most abundant EMF from this synthesis), Sc3 C2 @C80 , isomers of Sc2 C2 @C82 , and the family Sc2 C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3 CH@C80 . The Sc-Ti/CH4 system produces the mixed-metal Sc2 TiC@C2 n (2 n=68, 78, 80) and Sc2 TiC2 @C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition-metal-containing endohedral fullerenes, Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 , and Sc2 TiC2 @Ih -C80 , were characterized by NMR spectroscopy. The structure of Sc2 TiC@Ih -C80 was also determined by single-crystal X-ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2 TiC- and Sc2 TiC2 -containing clusterfullerenes have Ti-localized LUMOs. Encapsulation of the redox-active Ti ion inside the fullerene cage enables analysis of the cluster-cage strain in the endohedral fullerenes through electrochemical measurements.

  3. Gadolinium-uptake by aquatic and terrestrial organisms-distribution determined by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Lingott, Jana; Lindner, Uwe; Telgmann, Lena; Esteban-Fernández, Diego; Jakubowski, Norbert; Panne, Ulrich

    2016-02-01

    Gadolinium (Gd) based contrast agents (CA) are used to enhance magnetic resonance imaging. As a consequence of excretion by patients and insufficient elimination in wastewater treatment plants they are detected in high concentrations in surface water. At present, little is known about the uptake of these species by living organisms in aquatic systems. Therefore the uptake of gadolinium containing chelates by plants and animals grown in exposed water or on soil irrigated with exposed water was investigated. For this purpose two types of plants were treated with two different contrast agents. The uptake of the Gd contrast agents was studied by monitoring the elemental distribution with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). This technique allows the multi-elemental analysis of solid samples with high resolution and little sample preparation. The analysis of L. minor showed that the uptake of Gd correlated with the concentration of gadodiamide in the water. The higher the concentration in the exposed water, the larger the Gd signal in the LA-ICP-MS acquired image. Exposure time experiments showed saturation within one day. The L. minor had contact with the CAs through roots and fronds, whereas the L. sativum only showed uptake through the roots. These results show that an external absorption of the CA through the leaves of L. sativum was impossible. All the analyzed parts of the plant showed Gd signal from the CA; the highest being at the main vein of the leaf. It is shown that the CAs can be taken up from plants. Furthermore, the uptake and distribution of Gd in Daphnia magna were shown. The exposure via cultivation medium is followed by Gd signals on the skin and in the area of the intestine, while the uptake via exposed nutrition algae causes the significantly highest Gd intensities in the area of the intestine. Because there are hints of negative effects for human organism these findings are important as they show that Gd based

  4. Adherence to MRI protocol consensus guidelines in multiple sclerosis: an Australian multi-centre study.

    PubMed

    Curley, Michael; Josey, Lawrence; Lucas, Robyn; Dear, Keith; Taylor, Bruce V; Coulthard, Alan; Chapman, Caron; Coulthard, Alan; Dear, Keith; Dwyer, Terry; Kilpatrick, Trevor; Lucas, Robyn; McMichael, Tony; Pender, Michael P; Ponsonby, Anne-Louise; Taylor, Bruce; Valery, Patricia; van der Mei, Ingrid; Williams, David

    2012-12-01

    Multiple sclerosis (MS) is a debilitating disease that causes significant morbidity within a young demographic. Diagnostic guidelines for MS have evolved, and imaging has played an increasingly important role in diagnosis over the last two decades. For imaging to contribute to diagnosis in a meaningful way, it must be reproducible. Consensus guidelines for MRI in MS exist to define correct sequence type and imaging technique, but it is not clear to what extent they are followed. This study reviewed MRI studies performed on Australian individuals presenting with a first clinical diagnosis of central nervous system demyelination (FCD) for adherence to published guidelines and discussed practical implementation of MS guidelines in light of recent updates. The Ausimmune study was a prospective case control study of Australian participants presenting with FCD from 2003 to 2006. Baseline cranial and spinal cord MRI studies of 226 case participants from four separate Australian regions were reviewed. MRI sequences were classified according to anatomical location, slice plane, tissue weighting and use of gadolinium-containing contrast media. Results were compared with the 2003 Consortium of Multiple Sclerosis Centres MRI protocol for the diagnosis of MS. The composition of core cranial MRI sequences performed varied across the 226 scans. Of the studies, 91% included sagittal fluid attenuated inversion recovery (FLAIR) sequences. Cranial axial T2-weighted, axial FLAIR and axial proton density-weighted sequences were performed in 88%, 60% and 16% (respectively) of scans. Only 25% of the studies included a T1-weighted contrast-enhanced sequence. Concordance with the guidelines in all sequences was very low (2). Only a small number of MRI investigations performed included all of the sequences stipulated by consensus guidelines. This is likely due to poor awareness in the imaging community of the guidelines and the rationale behind certain sequences. Radiologists with a sub

  5. The distribution of anthropogenic REE in the Dutch distributaries of the Rhine: the role of suspended matter

    NASA Astrophysics Data System (ADS)

    Roskam, Gerlinde; Verheul, Marc; Klaver, Gerard; Bakker, Ingrid

    2014-05-01

    In nature rare earth elements (REE) occur in fixed ratios; contamination with a single rare earth element causes a clear deviation from the natural NASC normalized REE-patterns: an anomaly. REE are progressively used in many high technology products and processes. For example, gadolinium-containing chelates have been used since the '80s as contrasting agent in MRI-imaging. The pertaining anomaly is currently used as a tracer for distinguishing waste water from water unaffected by anthropogenic contamination. In the Dutch monitoring program in the Rhine-Meuse distributaries, total (10% HNO3 digested) and dissolved (< 0.45 µm) fractions in surface water are routinely analysed, and with two-week intervals suspended matter samples are collected with a centrifuge. Since 2008, the set of analysed elements was extended with REE, enabling this study. Lobith, the entry point of the River Rhine in The Netherlands, shows an annual oscillation in the magnitude of the lanthanum (La) anomaly. This positive La-anomaly was reported by Kulaksiz and Bau in 2011; they identified the point source as a production plant for catalysts used in petroleum refining in the German city of Worms. Since the spring of 2011, samarium (Sm) is used in the same process, resulting in matching La- and Sm-anomalies. The anthropogenic La and Sm concentrations are predominantly present in the total fraction, which suggests that the anthropogenic La and Sm concentrations are associated with suspended matter. The anthropogenic La and Sm concentrations are lower in the suspended matter samples collected with the centrifuge, suggesting a bias of these La and Sm concentrations in the finer fraction of the suspended matter. The anthropogenic La en Sm concentrations remain relatively constant throughout the rivers, but close to Lake IJsselmeer and the North Sea, sedimentation causes a sharp decrease in the anthropogenic concentrations. Detailed sampling of sediments, suspended matter and water could give a

  6. A Review of Quantum Confinement

    SciTech Connect

    Connerade, Jean-Patrick

    2009-12-03

    A succinct history of the Confined Atom problem is presented. The hydrogen atom confined to the centre of an impenetrable sphere counts amongst the exactly soluble problems of physics, alongside much more noted exact solutions such as Black Body Radiation and the free Hydrogen atom in absence of any radiation field. It shares with them the disadvantage of being an idealisation, while at the same time encapsulating in a simple way particular aspects of physical reality. The problem was first formulated by Sommerfeld and Welker - henceforth cited as SW - in connection with the behaviour of atoms at very high pressures, and the solution was published on the occasion of Pauli's 60th birthday celebration. At the time, it seemed that there was not much other connection with physical reality beyond a few simple aspects connected to the properties of atoms in solids, for which more appropriate models were soon developed. Thus, confined atoms attracted little attention until the advent of the metallofullerene, which provided the first example of a confined atom with properties quite closely related to those originally considered by SW. Since then, the problem has received much more attention, and many more new features of quantum confinement, quantum compression, the quantum Faraday cage, electronic reorganisation, cavity resonances, etc have been described, which are relevant to real systems. Also, a number of other situations have been uncovered experimentally to which quantum confinement is relevant. Thus, studies of the confined atom are now more numerous, and have been extended both in terms of the models used and the systems to which they can be applied. Connections to thermodynamics are explored through the properties of a confined two-level atom adapted from Einstein's celebrated model, and issues of dynamical screening of electromagnetic radiation by the confining shell are discussed in connection with the Faraday cage produced by a confining conducting shell. The

  7. A Review of Quantum Confinement

    NASA Astrophysics Data System (ADS)

    Connerade, Jean-Patrick

    2009-12-01

    A succinct history of the Confined Atom problem is presented. The hydrogen atom confined to the centre of an impenetrable sphere counts amongst the exactly soluble problems of physics, alongside much more noted exact solutions such as Black Body Radiation and the free Hydrogen atom in absence of any radiation field. It shares with them the disadvantage of being an idealisation, while at the same time encapsulating in a simple way particular aspects of physical reality. The problem was first formulated by Sommerfeld and Welker [1]—henceforth cited as SW—in connection with the behaviour of atoms at very high pressures, and the solution was published on the occasion of Pauli's 60th birthday celebration. At the time, it seemed that there was not much other connection with physical reality beyond a few simple aspects connected to the properties of atoms in solids, for which more appropriate models were soon developed. Thus, confined atoms attracted little attention until the advent of the metallofullerene, which provided the first example of a confined atom with properties quite closely related to those originally considered by SW. Since then, the problem has received much more attention, and many more new features of quantum confinement, quantum compression, the quantum Faraday cage, electronic reorganisation, cavity resonances, etc have been described, which are relevant to real systems. Also, a number of other situations have been uncovered experimentally to which quantum confinement is relevant. Thus, studies of the confined atom are now more numerous, and have been extended both in terms of the models used and the systems to which they can be applied. Connections to thermodynamics are explored through the properties of a confined two-level atom adapted from Einstein's celebrated model, and issues of dynamical screening of electromagnetic radiation by the confining shell are discussed in connection with the Faraday cage produced by a confining conducting shell

  8. Biologically-compatible gadolinium(at)(carbon nanostructures) as advanced contrast agents for magnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Sitharaman, Balaji

    2005-11-01

    Paramagnetic gadolinium-based carbon nanostructures are introduced as a new paradigm in high-performance magnetic resonance imaging (MRI) contrast agent (CA) design. Two Gd C60-based nanomaterials, Gd C60 [C(COOH)2]10 and Gd C60(OH)x are shown to have MRI efficacies (relaxivities) 5 to 20 times larger than any current Gd3+-based CA in clinical use. The first detailed and systematic physicochemical characterization was performed on these materials using the same experimental techniques usually applied to traditional Gd 3+-based CAs. Water-proton relaxivities were measured for the first time on these materials, as a function of magnetic field (5 x 10-4--9.4 T) to elucidate the different interaction mechanisms and dynamic processes influencing the relaxation behavior. These studies attribute the observed enhanced relaxivities completely to the "outer sphere" proton relaxation mechanism. These "outer sphere" relaxation effects are the largest reported for any Gd3+-based agent without inner-sphere water molecules. The proton relaxivities displayed a remarkable pH-dependency, increasing dramatically with decreasing pH (pH: 3--12). The increase in relaxivity resulted mainly from aggregation and subsequent three-order-of-magnitude increase in tauR, the rotational correlation time. Water-soluble fullerene materials (such as the neuroprotective fullerene drug, C3) readily cross cell membranes, suggesting an application for these gadofullerenes as the first intracellular, as well as pH-responsive MRI CAs. Studies performed at 60 MHz in the presence of phosphate-buffered saline (PBS, mice serum pH: 7.4) to mimic physiological conditions demonstrated that the aggregates can be disrupted by addition of salts, leading to a decrease in relaxivity. Biological fluids present a high salt concentration and should strongly modify the behavior of any fullerenes/metallofullerene-based drug in vivo. Gd C60[C(COOH)2]10 also showed enhanced relaxivity (23% increase) in the presence of the

  9. Trimetallic nitride endohedral C80 fullerenes and their application in Organic Photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Ross, Russel Brett

    Trimetallic nitride endohedral C80 fullerenes (TNEF) materials offer a reduced lowest unoccupied molecular orbital energy (LUMO) offset when compared with many of the polymer donor systems currently being employed in Organic Photovoltaic (OPV) research. This lower LUMO offset allows for higher open circuit voltages, and therefore, higher efficiencies in OPV devices. Presented here is a comprehensive study of the room temperature absorption and emission of a series of trimetallic nitride endohedral metallofullerenes, M3N C80, (M = Er, Gd, Ho, Lu, Sc, Y), as well the investigation and demonstration of TNEFs use as an acceptor material in OPV devices. Morphology and electrode contacts are shown to have large influence on TNEF-based OPV performance, in poly(3-hexyl)thiophene (P3HT) and 1-(3-hexoxycarbonyl)propyl-1-phenyl-[6,6]-Lu3N C81 (Lu3N C80-PCBH) based OPV devices. Decreasing the LUMO offset between P3HT and the acceptor material, reduced energy losses in the charge transfer process, which yield an increased open circuit voltage to 280mV above reference devices made with P3HT & [6,6]-phenyl-C61-butyric methyl ester (C60-PCBM). OPV energy conversion efficiencies of > 4% are observed with P3HT/Lu3N C80-PCBH active layer with a predicted upper limit on power conversion efficiency of > 6% for this donor/acceptor system. The data displayed within this work constitutes proof of concept that the varying reduction potential (160--290 meV vs. C 60-PCBM) of the TNEF acceptor molecules provides a pathway to enhancing OPV device performance by closing down the molecular orbital offset of the donor/acceptor heterojunction. TNEF acceptor materials in single bulk heterojunction devices offer a viable path to 11% conversion efficiency with already-reported-on low-band-gap donors, such as poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)- alt-4,7-(2,1,3-benzothiadiazole), PCPDTBT.

  10. Endohedral metal atoms in pristine and functionalized fullerene cages.

    PubMed

    Yamada, Michio; Akasaka, Takeshi; Nagase, Shigeru

    2010-01-19

    Fullerene, an allotropic form of carbon made up of spherical molecules formed from pentagonal and hexagonal rings, was first discovered in 1985. Because fullerenes have spacious inner cavities, atoms and clusters can be encapsulated inside the fullerene cages to form endohedral fullerenes. In particular, the unique structural and electronic properties of endohedral metallofullerenes (EMFs), where metal atoms are encapsulated within the fullerene, have attracted wide interest from physicists and chemists as well as materials scientists and biologists. The remarkable characteristics of these molecules originate in the electron transfer from the encapsulated metal atoms to the carbon cage. The positions and movements of the encapsulated metal atoms are important determinants of the chemical and physical properties of EMFs. In this Account, we specifically describe the positions and dynamic behavior of the metal atoms encapsulated in pristine and functionalized fullerene cages. First, we examined whether the metal atoms are attached rigidly to cage carbons or move around. Our systematic investigations of EMFs, including M@C(2v)-C(82), M(2)@D(2)(10611)-C(72), M(2)@D(3h)(5)-C(78), M(2)@I(h)-C(80), and M(2)@D(5h)-C(80), revealed that the metal positions and movements vary widely with different cage structures and numbers of metal atoms. Second, we wanted to understand whether we could control the positions and movements of the untouchable metal atoms in EMFs. One possible way to modulate this behavior was through attachment of a molecule to the outer surface of the cage. We developed synthetic methods to modify EMFs and have examined the metal positions and movements in the functionalized carbon cages. Remarkably, we could alter the dynamic behavior of the encaged metal atoms in M(2)@I(h)-C(80) drastically through chemical modification of the outer cage. We anticipate that the control of metal atom structures and dynamics within a cage could be valuable for designing

  11. Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

    PubMed

    Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

    2008-02-04

    Cu ion from the other unit. The magnetic properties of the gadolinium-containing complexes have been determined. Ferromagnetic exchange interactions within the trinuclear [Cu(2)Gd] motifs occur. In the compounds 4 and 7, the [Ni(mnt)(2)](*-) radical anions contribution to the magnetization is clearly observed in the high-temperature regime, and most of it vanishes upon temperature decrease, very likely because of the rather strong antiferromagnetic exchange interactions between the open-shell species. The extent of the exchange interaction in the compound 7, which was found to be antiferromagnetic, between the coordinated Cu center and the corresponding [Ni(mnt)(2)](*-) radical anion, bearing mostly a 3p spin type, was estimated through CASSCF/CASPT2 calculations. Compound 6 exhibits a slow relaxation of the magnetization.

  12. Optical limiting and degenerate four-wave mixing in novel fullerenes

    NASA Astrophysics Data System (ADS)

    Marciu, Daniela

    1999-09-01

    -triplet absorption cross-section at 700 nm, which is shifted from the 750 nm value for the C60 molecule. For the first time, optical limiting measurements are performed on five separate C 84 isomers. These intriguing results show that the optical limiting behavior is strongly dependent on the cage symmetry. It is also found that the most abundant isomer does not have the strongest optical limiting performance, but is in fact one of the weaker optical limiters of the isomers isolated so far. The nonresonant degenerate four-wave mixing experiments performed on the endohedral metallofullerene Er2@C82, at 1064 nm, show that the third order nonlinear susceptibility value is increased by orders of magnitude relative to the empty cage fullerenes, thus, confirming the charge-transfer process from the encapsulated atoms to the fullerene cage. We obtain a value g(3)x yyx(- w; w,w,- w)=-8.65×10 -32 esu for the molecular second order hyperpolarizability, which is almost three orders of magnitude larger than the values reported in literature for an empty cage fullerene. (Abstract shortened by UMI.)

  13. Interstellar fullerene compounds and diffuse interstellar bands

    NASA Astrophysics Data System (ADS)

    Omont, Alain

    2016-05-01

    Recently, the presence of fullerenes in the interstellar medium (ISM) has been confirmed and new findings suggest that these fullerenes may possibly form from polycyclic aromatic hydrocarbons (PAHs) in the ISM. Moreover, the first confirmed identification of two strong diffuse interstellar bands (DIBs) with the fullerene, C60+, connects the long standing suggestion that various fullerenes could be DIB carriers. These new discoveries justify reassessing the overall importance of interstellar fullerene compounds, including fullerenes of various sizes with endohedral or exohedral inclusions and heterofullerenes (EEHFs). The phenomenology of fullerene compounds is complex. In addition to fullerene formation in grain shattering, fullerene formation from fully dehydrogenated PAHs in diffuse interstellar clouds could perhaps transform a significant percentage of the tail of low-mass PAH distribution into fullerenes including EEHFs. But many uncertain processes make it extremely difficult to assess their expected abundance, composition and size distribution, except for the substantial abundance measured for C60+. EEHFs share many properties with pure fullerenes, such as C60, as regards stability, formation/destruction and chemical processes, as well as many basic spectral features. Because DIBs are ubiquitous in all lines of sight in the ISM, we address several questions about the interstellar importance of various EEHFs, especially as possible carriers of diffuse interstellar bands. Specifically, we discuss basic interstellar properties and the likely contributions of fullerenes of various sizes and their charged counterparts such as C60+, and then in turn: 1) metallofullerenes; 2) heterofullerenes; 3) fulleranes; 4) fullerene-PAH compounds; 5) H2@C60. From this reassessment of the literature and from combining it with known DIB line identifications, we conclude that the general landscape of interstellar fullerene compounds is probably much richer than heretofore realized

  14. A Milestone: Approval of CEUS for Diagnostic Liver Imaging in Adults and Children in the USA.

    PubMed

    Seitz, K; Strobel, D

    2016-06-01

    performed by an experienced examiner/clinician often provides the solution, particularly in the case of small lesions, and is the last resort before US-guided biopsy 45 46. However, there is a lack of competent CEUS examiners and Germany continues to be the world champion of X-ray examinations with no noticeable reverse trend. In almost every doctor's office and hospital, ultrasound costs are by far not fully covered, resulting in an extremely high frequency of CT use with CT being available to everyone regardless of insurance status.The USA is now in the starting position for CEUS. It will be exciting to see how the method will develop there. The FDA's decision to approve sulfur hexafluoride (Lumason(®) = SonoVue(®)) should be considered against the background of the radiation exposure caused by CT examinations and the fact that MRI using gadolinium-containing contrast agents is no longer considered noninvasive because of nephrogenic systemic fibrosis (NSF) and the accumulation of the agent in the cerebrum. An essential point of the campaign regarding the avoidance of diagnostic radiation exposure triggered in the USA by the publications of Brenner et al. 77 78 was that the agent was approved for use in the liver even for children 79 80 - still off label in Europe - without additional comprehensive studies due to the available scientific results and the very low side effects profile of Lumason(®) (= SonoVue(®)). It is admittedly unclear why other indications (except the heart which has been approved since 2014) are excluded even though the microbubbles as a pure blood pool contrast agent can be diagnostically used in the entire vascular system and bed of all organs. To our knowledge, there is no such restriction on the approval of X-ray contrast agents.Like echocardiography and emergency ultrasound, CEUS began in Europe but will probably only establish its final diagnostic value as a "reimport".This is a major opportunity to permanently define the role of

  15. Proceedings of the 9th International Symposium on Foundations of Quantum Mechanics in the Light of New Technology

    NASA Astrophysics Data System (ADS)

    Ishioka, Sachio; Fujikawa, Kazuo

    2009-06-01

    detection / T. Tanamoto, Y. Nishi, S. Fujita. Geometric universal single qubit operation of cold two-level atoms / H. Imai, A. Morinaga. Entanglement dynamics in quantum Brownian motion / K. Shiokawa. Coupling superconducting flux qubits using AC magnetic flxues / Y. Liu, F. Nori. Entanglement purification using natural spin chain dynamics and single spin measurements / K. Maruyama, F. Nori. Experimental analysis of spatial qutrit entanglement of down-converted photon pairs / G. Taguchi ... [et al.]. On the phase sensitivity of two path interferometry using path-symmetric N-photon states / H. F. Hofmann. Control of multi-photon coherence using the mixing ratio of down-converted photons and weak coherent light / T. Ono, H. F. Hofmann -- Mechanical properties of confined geometry. Rattling as a novel anharmonic vibration in a solid / Z. Hiroi, J. Yamaura. Micro/nanomechanical systems for information processing / H. Yamaguchi, I. Mahboob -- Precise measurements. Electron phase microscopy for observing superconductivity and magnetism / A. Tonomura. Ratio of the Al[symbol] and Hg[symbol] optical clock frequencies to 17 decimal places / W. M. Itano ... [et al.]. STM and STS observation on titanium-carbide metallofullerenes: [symbol] / N. Fukui ... [et al.]. Single shot measurement of a silicon single electron transistor / T. Ferrus ... [et al.]. Derivation of sensitivity of a Geiger mode APDs detector from a given efficiency to estimate total photon counts / K. Hammura, D. A. Williams -- Novel properties in nano-systems. First principles study of electroluminescence in ultra-thin silicon film / Y. Suwa, S. Saito. First principles nonlinear optical spectroscopy / T. Hamada, T. Ohno. Field-induced disorder and carrier localization in molecular organic transistors / M. Ando ... [et al.]. Switching dynamics in strongly coupled Josephson junctions / H. Kashiwaya ... [et al.]. Towards quantum simulation with planar coulomb crystals / I. M. Buluta, S. Hasegawa -- Fundamental problems in

  16. EDITORIAL: Opposites attract: nanomagnetism in theory and practice Opposites attract: nanomagnetism in theory and practice

    NASA Astrophysics Data System (ADS)

    Demming, Anna

    2012-09-01

    Applications of artificial intelligence for chemical inference. XVII. An approach to computer-assisted elucidation of molecular structure J. Am. Chem. Soc. 97 5755-62 [7] Saito S, Oshiyama A, Miyamoto Y, Hamada N and Sawada S 1992 Electronic structure of fullerenes and fullerides: artificial atoms and their solids Nanotechnology 3 167-72 [8] Shinohara H 2000 Endohedral metallofullerenes Rep. Prog. Phys. 63 843-92 [9] Heitmann D, Kern K, Demel T, Grambow P, Ploog K and Zhang Y H 1992 Spectroscopy of quantum dots and antidots Surf. Sci. 267 245-52 [10] Andergassen S, Meen V, Schoeller H, Splettstoesser J and Wegewijs M R 2010 Charge transport through single molecules, quantum dots and quantum wires Nanotechnology 21 272001 [11] Lim W H, Yang C H, Zwanenburg F A and Dzurak A S 2011 Spin filling of valley-orbit states in a silicon quantum dot Nanotechnology 22 335704