DOCSLIB.ORG

Dissertation Trifluoromethylated

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Dissertation Trifluoromethylated DISSERTATION TRIFLUOROMETHYLATED FULLERENES AND POLYCYCLIC AROMATIC HYDROCARBONS AND ANAEROBICALLY MILLED SILICON NANOPARTICLES Submitted by Karlee P. Castro Department of Chemistry In partial fulfillment of the requirements For the Degree of Doctor of Philosophy Colorado State University Fort Collins, Colorado Fall 2015 Doctoral Committee: Advisor: Steven. H. Strauss Melissa M. Reynolds Delphine K. Farmer Martin J. McCullagh Howard S. Ramsdell Copyright by Karlee P. Castro 2015 All Rights Reserved ABSTRACT TRIFLUOROMETHYLATED FULLERENES AND POLYCYCLIC AROMATIC HYDROCARBONS AND ANAEROBICALLY MILLED SILICON NANOPARTICLES Well characterized molecules and materials are essential to understand trends and predict future performance. Fundamental studies provide information about molecular properties which may be useful in other applications such as electronic devices. The focus of this dissertation is the characterization of three different classes of molecules/materials with the goal of understanding the fundamental underlying reasons for any trends observed. The first chapter of this dissertation examines the photophysical properties of C70(CF3)n (n = 8 or 10) molecules. Four of the compounds exhibited quantum yields higher than for any previously reported C70 derivative and three exceeded 0.24, the highest fluorescence quantum yield for any fullerene or fullerene derivative. A difference in the location of only one CF3 group in C70(CF3)8 and C70(CF3)10 isomers resulted in 200-fold and 14-fold increases in fluorescence quantum yields respectively. The isomer of C70(CF3)10 with the highest fluorescence quantum yield (0.68 in toluene) also exhibited the longest fluorescence lifetime (51 ns). Formation of the S1 state in one of the C70(CF3)10 isomers occurred within 0.6 ps and its nanosecond-long decay was monitored by ultrafast transient absorption spectroscopy. Time-dependent density functional theory calculations provide a physically meaningful understanding of the photophysical properties. High fluorescence quantum yields are correlated with high oscillator strengths for the S0→S1 transition, large ΔS1−T1 energy gaps, and small spatial extension of the S0→S1 excitation. The second chapter of this dissertation explores trifluoromethyl derivatives of polycyclic aromatic hydrocarbons (PAH(CF3)n). First, the effects of PAH size and shape on the product distribution are examined. Second, the electronic properties, including reduction potential and ii gas-phase electron affinity, are examined. Third, the influence of number and orientation of the CF3 groups on the crystalline morphologies of these compounds is explored. Finally, charge- transfer complexes made with PAH(CF3)n molecules mixed with PAHs are prepared and examined spectroscopically and crystallographically. From this work it was determined that when PAHs with 8–10 substitutable carbons are reacted with at least 10 equivalents of CF3I gas the PAH(CF3)n products had n values of 4–6 regardless of the size or shape of the PAH core. The reduction potential and gas-phase electron affinity exhibit a regular, incremental increase as a function of the number of trifluoromethyl groups. The number and position of CF3 groups influences the π-π stacking and crystalline morphologies and typically the more CF3 groups added, the lower the intermolecular overlap. Charge-transfer complexes made from mixing PAH(CF3)n and PAH form mixed stacks in the solid-state and exhibit weak association constants in solution. The third chapter of this dissertation examines the effects of oxygen and aromatic molecules on stirred media milling of silicon. Metallurgical-grade silicon was wet-milled in a stirred media mill to produce nanoparticles. Several milling fluids, additives, and milling parameters have been tested and compared between aerobic and anaerobic milling. It was determined that oxygen and aromatic molecules serve as surface passivating additives and lead to higher specific surface areas, indicating smaller particles. Particle amorphization occurs rapidly in a stirred media mill, within two hours crystallite size is on the order of 2-50 nm regardless of whether surface passivating additives are present. In all milling experiments, even in the presence of oxygen, new Si–C bonds are formed, the most Si–C bonds are formed when aromatic molecules are present during the milling process. iii ACKNOWLEDGMENTS First and foremost I would like to thank my husband, Rick. You supported me from the time I declared I wanted to quit my job and go to graduate school and you’ve kept supporting me through all the ups and downs of the process. Thank you for being my design consultant. I truly appreciate all the hard work you have put in to put me through school twice now. You are the best and have done so much for me I can’t list it all. The past and present members of the Strauss-Boltalina research group have enriched my graduate school experience. Eric V. Bukovsky has been an excellent collaborator on multiple projects, diagnosed my shingles, got most of my Simpsons references, and didn’t get too upset when I rained on his parades. Long K. San always answered my random question text messages, sent out morale boosting funny e-mails, and tried to make the lab a cleaner place. Tyler T. Clikeman always has (or at least pretends to have) an excellent attitude and he’s always willing to help. Thanks to all three of you for showing me how graduate school is done. Brent M. Wyatt brought me coupon books and root beer and was there with me on the longest day of graduate school. No less important are those who helped me get through the first couple of years: Amanda M. Pluntze, Dr. Bryon W. Larson, and Dr. Igor V. Kuvychko. Thanks for the advice, the fun, and the camaraderie. Thank you to the unofficial Strauss-Boltalina group member Desirée Bukovsky for giving me a home away from home. My sincere appreciation goes to my advisors Prof. Steven H. Strauss and Dr. Olga V. Boltalina. You believe in me more than I believe in myself. Olga has been indispensible with reading drafts, ideas for experiments, general support, and so much more. Steve pushes for the best, finds new angles in my research that I have overlooked, and has boundless enthusiasm for science. Thank you for the baked goods and pizza at group meetings and group trips to Breckenridge. I appreciate that you accepted my commuting and were understanding of the resulting odd schedules. iv Excellent collaborators have made my work possible. Dr. Jeffrey J. Rack and Dr. Yuhuan Jin were excellent hosts in Ohio an instrumental in making time-resolved spectroscopic measurements. Dr. Alexey A. Popov provided theoretical calculations and spearheaded the writing of the fullerene fluorophores paper. Dr. Xue-Bin Wang and co-workers measured gas- phase electron affinities. Dr. Yu-Sheng Chen hosted the Synchrotron Charge Density School and assisted a number of my colleagues with synchrotron X-ray crystallography. Dr. Andrew J. Ferguson and Dr. Jeffrey L. Blackburn taught me how to use the instrument I used to collect singlet oxygen quantum yields and were very accommodating every time I wanted to come back and do more measurements. Dr. Stephen A. Rolfe and Dr. Andrew J. Fleming presented the idea of using fluorescent fullerenes as leaf imaging agents and their co-workers completed the proof of concept testing. My family provides much needed love and support. I don’t think I can ever adequately express my gratitude to or repay my mom for all she has done for me. Thank you to my dad for being interested in my work, helping try out ideas for science projects for elementary school students, and the AAA membership which provided peace of mind for my commutes. Thank you to my cousin, Amanda Faux, for packing up her kids and driving me to Fort Collins to see the eye doctor. Thank you to the rest of my family and Rick’s family for all the ways you have helped me through the years. I want to acknowledge my friends who have supported me for years. To all the other raging balls of angry smart kids thanks for starting my cult and continuing to support me. Thanks in particular to Heather Gannon for editing this dissertation, any mistakes are mine and were made after her deft editing. My dear friend Sara Allen has leant her ear and her pen and has inspired me. Joyce Miyagishima, thank you for being a great aisle-mate and friend (FPS). Erin Stuckert and Morgan Hawker threw me a birthday party when I really needed it, always attended my practice talks, discussed science with me, and shared my enjoyment of game nights. My committee members have been excellent teachers. Thank you for both scientific discussions and practical graduate school advice. Thank you to all of the support staff in the CSU v Department of Chemistry. You all do a million things and I’m sure I don’t even know half of what you do. Korina Brim and Karen Kahler were especially helpful at the end of a trying project and Korina provided some much needed laughs. I appreciate Dr. Johnna Bontadelli in the CSU Health Network for helping save my sight when I had shingles. I would like to acknowledge my undergraduate professors who got me interested in chemistry. Dr. Eric Ball was the best instructor I ever had and helped cement my interest in analytical and inorganic chemistry. Thanks to Dr. Niels Schonbeck for making me think, exposing me to new ideas, and encouraging my continued education. Dr. Susan Schelble helped me to become the first student at Metro to complete an honors thesis in chemistry and encouraged me to attend graduate school. Thank you to the artists who helped me get through graduate school without even knowing it. These include Cold Cave, Depeche Mode, Nitzer Ebb, Joy Division, the team behind Orphan Black, the team behind The Simpsons, Wolf Pupy, Neil Gaiman, William Gibson, and others I’m sure I forgot.
Load more

Recommended publications
  • Calorimetric Studies of Solvates of C60 and C70 with Aromatic Solvents
    J. Phys. Chem. B 1999, 103, 1339-1346 1339 Calorimetric Studies of Solvates of C60 and C70 with Aromatic Solvents Mikhail V. Korobov, Andrej L. Mirakyan, and Natalia V. Avramenko Department of Chemistry, Moscow State UniVersity, 119899 Moscow, Russia Gerd Olofsson* Thermochemistry DiVision, Center for Chemistry and Chemical Engineering, Lund UniVersity, S-22100 Lund, Sweden Allan L. Smith* Chemistry Department, Drexel UniVersity, Philadelphia, PennsylVania 19104 Rodney S. Ruoff Physics Department, Washington UniVersity, St. Louis, Missouri 63130 ReceiVed: July 24, 1998; In Final Form: December 18, 1998 To improve the understanding of the solution properties of C60 and C70 in aromatic solvents, binary systems of C60 and C70 with benzene, toluene, 1,2- and 1,3-dimethylbenzene, 1,2,4- and 1,3,5-trimethylbenzene, bromobenzene, and 1,2- and 1,3-dichlorobenzene were studied using differential scanning calorimetry, solution calorimetry, and thermogravimetry. Solid solvates with different compositions were identified in many of the systems. The solvates were characterized by composition and by the temperature and the enthalpy of the incongruent melting transition. Enthalpies of solution of C60 in toluene, 1,2-dimethylbenzene, 1,2- and 1,3- dichlorobenzene, and 1,2,4-trimethylbenzene and of C70 in 1,2-dimethylbenzene and in 1,2- and 1,3- dichlorobenzene were determined. The formation-incongruent melting of solid solvates causes maxima in the temperature-solubility curves of fullerenes in aromatic solvents. Trends in solubility behavior of fullerenes were discussed in terms of thermodynamics of solution and solvate formation. Introduction solvate (II), or more probably, pure C60. Phase equilibrium conditions relate the mole fraction of C60, x(C60), to T (tem- The unusual temperature dependence of solubility of fullerenes perature) for both low- and high-temperature parts of the (ln x)- 1 in a number of solvents has attracted attention and provoked T curve.
    [Show full text]
  • Polymer Solar Cells Based on Poly(3-Hexylthiophene) and Fullerene: Pyrene Acceptor Systems
    Polymer solar cells based on poly(3-hexylthiophene) and fullerene: Pyrene acceptor systems a a a a, * Alessandra Cominetti , Andrea Pellegrino , Luca Longo , Riccardo Po , Alessandra a a a b, 1 Tacca , Chiara Carbonera , Mario Salvalaggio , Michele Baldrighi , Stefano Valdo b Meille a Research Center for Renewable Energies and Environment, Istituto Donegani, Eni S.p.A, Via Fauser 4, IT-28100 Novara, Italy b Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”, Politecnico di Milano, via Mancinelli 7, IT-20131 Milano, Italy Received 12 May 2014 Received in revised form 30 January 2015 Accepted 27 March 2015 Available online 4 April 2015 1. Introduction The literature on novel materials for polymer solar cells [1e3] deals mainly with the development of the donor components of the active layer [4e9], while much fewer papers are devoted to novel acceptors [10,11]. [6,6]-phenyl-C61-butyric acid methyl ester * Corresponding author. E-mail address: [email protected] (R. Po). 1 Present address: Istituto Italiano di Tecnologia (IIT), via Morego 30, IT-16163 Genova, Italy. (PCBM) is the oldest [12], the most used [13] and, to date, still one filtered, and the solvent was distilled under reduced pressure. 1.03 g of the most effective acceptors for bulk heterojunction polymer (yield 84%) of a pale yellow oil were obtained, which became a solar cells. The popularity of PCBM, aside from its unique electronic white solid after 24 h of storage at þ4 C in a refrigerator. ¼ 1 0 properties, is mainly due to its good solubility in many organic Tm 37.4 C (DSC).
    [Show full text]
  • Decontamination of Surfaces Exposed to Carbon-Based Nanotubes and Nanomaterials
    Hindawi Publishing Corporation Journal of Nanomaterials Volume 2014, Article ID 249603, 9 pages http://dx.doi.org/10.1155/2014/249603 Research Article Decontamination of Surfaces Exposed to Carbon-Based Nanotubes and Nanomaterials Paul Su,1 Babak Haghpanah,2 William W. Doerr,1 Zahra Karimi,2 Syed Hassan,2 Louis Gritzo,1 Ahmed A. Busnaina,2 and Ashkan Vaziri2 1 FMGlobal,Norwood,MA02062,USA 2 DepartmentofMechanicalandIndustrialEngineering,NortheasternUniversity,Boston,MA02115,USA Correspondence should be addressed to Paul Su; [email protected] Received 10 October 2013; Accepted 12 December 2013; Published 16 January 2014 Academic Editor: Aiying Wang Copyright © 2014 Paul Su et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Contamination of surfaces by nanomaterials can happen due to accidental spillage and release or gradual accumulation during processing or handling. Considering the increasingly wide use of nanomaterials in industry and research labs and also taking into account the diversity of physical and chemical properties of different nanomaterials (such as solubility, aggregation/agglomeration, and surface reactivity), there is a pressing need to define reliable nanomaterial-specific decontamination guidelines. In this paper, we propose and investigate a potential method for surface decontamination of carbon-based nanomaterials using solvent cleaning and wipes. The results show that the removal efficiency for single- and multiwalled carbon nanotubes from silicon wafers sprayed with water-surfactant solutions prior to mechanical wiping is greater than 90% and 95%, respectively. The need for further studies to understand the mechanisms of nanomaterial removal from surfaces and development of standard techniques for surface decontamination of nanomaterials is highlighted.
    [Show full text]
  • Ep 2 098 549 A1
    (19) & (11) EP 2 098 549 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 09.09.2009 Bulletin 2009/37 C08G 61/00 (2006.01) C01B 31/02 (2006.01) C09D 201/02 (2006.01) H01L 51/30 (2006.01) (2006.01) (21) Application number: 07860265.3 H01L 51/42 (22) Date of filing: 26.12.2007 (86) International application number: PCT/JP2007/075036 (87) International publication number: WO 2008/081845 (10.07.2008 Gazette 2008/28) (84) Designated Contracting States: (72) Inventors: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • TANAKA, Katsutomo HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE Kitakyusyu-shi SI SK TR Fukuoka 806-0004 (JP) • TAKAGI, Masatoshi (30) Priority: 27.12.2006 JP 2006351751 Yokohama-shi Kanagawa 227-8502 (JP) (71) Applicants: • Frontier Carbon Corporation (74) Representative: Vossius & Partner Fukuoka 806-0004 (JP) Siebertstraße 4 • Mitsubishi Chemical Corporation 81675 München (DE) Tokyo 108-0014 (JP) (54) FULLERENE FILM USING FULLERENE DERIVATIVE AS RAW MATERIAL, FULLERENE POLYMER AND THEIR PRODUCTION METHODS (57) A fullerene film and a fullerene polymer both produced from a fullerene derivative are provided which can be easily formed by a wet process and can retain the intact properties inherent in the fullerene. Also provided are processes for producing the film and polymer. A solution of a fullerene derivative decomposing at a temperature lower than the pyrolysis temperature of the fullerene, e.g., the fullerene derivative represented by the following formula, is applied to a substrate.
    [Show full text]
  • Dispersion of Fullerenes in Natural Water and Their
    DISPERSION OF FULLERENES IN NATURAL WATER AND THEIR BEHAVIOR IN WATER TREATMENT PROCESS A Thesis Presented to The Academic Faculty by Hoon Hyung In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Civil and Environmental Engineering Georgia Institute of Technology August 2008 DISPERSION OF FULLERENES IN NATURAL WATER AND THEIR BEHAVIOR IN WATER TREATMENT PROCESS Approved by: Dr. Jae-Hong Kim, Advisor Dr. Seung Soon, Jang School of Civil and Environmental School of Material Science and Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Joseph B. Hughes Dr. Vernon L. Snoeyink School of Civil and Environmental School of Civil and Environmental Engineering Engineering Georgia Institute of Technology University of Illinois Dr. Michael H. Bergin School of Civil and Environmental Engineering Georgia Institute of Technology Date Approved: June 11, 2008 [To Se-Eun and Juhee] ACKNOWLEDGEMENTS Firstly, I would like to thank my advisor, Dr. Jae-Hong Kim. He not only provided me a chance to become a piece of this great legacy of Georgia Tech., but also showed me the example of a great advisor with extensive knowledge, creative mind, and friendliness. I acknowledge my thesis committee, Dr. Joseph Hughes, Dr. Vernon Snoeyink, Dr. Michael Bergin, and Dr. Seung Soon Jang for agreeing to be my committee and providing invaluable comments and advices on my research. All the members of Dr. Kim and Dr. Huang’s groups and Korean graduate students in the environmental engineering program are greatly appreciated. It was very nice to share friendship with them in and out of the campus and discussions and advices from them brought me valuable idea on my research.
    [Show full text]
  • Sponge-Like Molecular Cage for Purification of Fullerenes
    ARTICLE Received 24 May 2014 | Accepted 13 Oct 2014 | Published 26 Nov 2014 DOI: 10.1038/ncomms6557 Sponge-like molecular cage for purification of fullerenes Cristina Garcı´a-Simo´n1, Marc Garcia-Borra`s1, Laura Go´mez1,2, Teodor Parella3,Sı´lvia Osuna1, Jordi Juanhuix4, Inhar Imaz5, Daniel Maspoch5,6, Miquel Costas1 & Xavi Ribas1 Since fullerenes are available in macroscopic quantities from fullerene soot, large efforts have been geared toward designing efficient strategies to obtain highly pure fullerenes, which can be subsequently applied in multiple research fields. Here we present a supramolecular nanocage synthesized by metal-directed self-assembly, which encapsulates fullerenes of different sizes. Direct experimental evidence is provided for the 1:1 encapsulation of C60, C70,C76,C78 and C84, and solid state structures for the host–guest adducts with C60 and C70 have been obtained using X-ray synchrotron radiation. Furthermore, we design a washing- based strategy to exclusively extract pure C60 from a solid sample of cage charged with a mixture of fullerenes. These results showcase an attractive methodology to selectively extract C60 from fullerene mixtures, providing a platform to design tuned cages for selective extraction of higher fullerenes. The solid-phase fullerene encapsulation and liberation represent a twist in host–guest chemistry for molecular nanocage structures. 1 Institut de Quı´mica Computacional i Cata`lisi and Departament de Quı´mica, Universitat de Girona, Campus Montilivi, Girona, Catalonia 17071, Spain. 2 Serveis Te`cnics de Recerca (STR), Universitat de Girona, Parc Cinetı´fic i Tecnolo`gic, Girona, Catalonia 17003, Spain. 3 Servei de RMN and Departament de Quı´mica, Facultat de Cie`ncies, Universitat Auto`noma de Barcelona (UAB), Campus UAB, Bellaterra, Catalonia 08193, Spain.
    [Show full text]
  • Extraction of Fullerenes in Organic Solvents and the Development of Superior Isolation Procedures
    Indian Journal of Chemistry Vol 31 MD, May 1992, pp. F32-F35 Extraction of fullerenes in organic solvents and the development of superior isolation procedures R Dhamodaran, I Kaliappam, N Sivaraman, T G Srinivasan, P R Vasudeva Rao & C K Mathews" Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, Tamil Nadu, India Received 20 February 1992 Development of methods for the isolation of fullerenes depends to a great extent on the identifica- tion of suitable solvents. In the present work, extraction of fuUerenes from carbon soot by a number of aliphatic, alicyclic and aromatic solvents has been examined at a constant temperature of 60°C. The results indicate that the extraction power of aliphatic straight chain hydrocarbons increases with in- crease in carbon chain length. The aromatic solvents have superior extracting power as compared to the aliphatic solvents. The higher extraction power of the aromatic solvents is attributed to their better solubilising action. Based on the experimental data, it was possible to develop efficient procedures for the chromatographic separation of C60 and C70 employing cyclohexane and a normal paraffin hydro- carbon mixture with average carbon number of 12 as solvents. C60 and C70 could both be isolated completely in pure form in much smaller volumes of eluant than in the hexane system. The recent isolation of macroquannnes of C60 makes this separation procedure tedious, and and C70 bas led to a veritable explosion in scien- large volumes of solutions have to be handled. tific literature on the properties of these all-car- Further, the use of toluene means that for recycl- bon clusters called fullerenes.
    [Show full text]
  • Solvatochromism, Aggregation and Photochemical Properties of Fullerenes, C60 and C70, in Solution
    Journal of Photoscience (2003), Vol. 10(1), pp. 105−119 Solvatochromism, Aggregation and Photochemical Properties of Fullerenes, C60 and C70, in Solution Sukhendu Nath, Haridas Pal, Avinash. V. Sapre* and Jai. P. Mittal Chemistry Group, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India Fullerenes, C60 and C70, display interesting physicochemical properties in solutions, especially due to their unique chemical structures and their good electron accepting abilities. Solubility of fullerenes in different organic solvents and their unusual solvatochromic behavior, the ability of the fullerenes to form aggregates in solutions, and their electron transfer and charge transfer interactions with variety of electron donors, are the subjects of extensive research activities for more than one decade. Many research groups including ours have contributed substantially in the understanding of the solvatochromism, aggregation behavior, and the photoinduced electron transfer and charge transfer chemistry of fullerenes, in condensed phase. Present article is aimed to summarize the important results reported on the above aspects of fullerenes, subsequent to the earlier report from our group (D.K. Palit and J.P. Mittal, Full. Sci. & Tech. 3, 1995, 643-659). key words: Fullerene, Solvatochromism, Aggregation, Electron Transfer, Charge Transfer, Exciplex, CT Complex INTRODUCTION exotic three-dimensional structure of fullerenes with spherical hollow cage is responsible for their extraordinary behavior in Since the separation of the fullerenes, C60 and C70, in solution. Their ability to act as electron relays and to generate macroscopic quantities from the soots [1], extensive studies long lived excited states has made them an important class of have been carried out on the scientific and technological photochemically active compounds.
    [Show full text]
  • Thermally Metastable Fullerenes
    THERMALLY METASTABLE FULLERENES IN FLAMES BY TAPESH KUMAR YADAV Subnutted to the Department of Cherical Engineering in partial fulfillment of the requirements for the degree of DOCTOR OF PHELOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY May 1994 1994 Massachusetts Institute of Technology All rights reserved Signature of Author j;/ I,- -, I I - IV - , I-4)eMl --------t of Chemical- Engineering March 10, 1994 Certified by Jack B. Howard I---- Thesis Supervisor Accepted by !;dence RobertETohen "" Department Committee for Graduate Students JUN 6 994 Thermally Metastable Fullerenes in Flames by Tapesh Yadav Submitted to the Department of Chemical Engineering on March 10, 1994 in partial fulfillment of the requirements for the Degree of Philosophy in Chemical Engineering. ABSTRACT Fullerenes are closed caged molecules of pure carbon. These carbon molecules are produced in abundant quantities by certain sooting processes. In particular, fullerenes are observed in large quantities in the soot produced by low pressure (100 Torr), inert environment, vaporization of pure carbon and in the soot produced by low pressure 40 Torr) laminar combustion of premixed benzene/oxygen/inert vapors. Along with the observation of large quantities of fullerenes, many more observations can be made from the soot of the two processes. One particularly significant observation is the presence of many thermally metastable fullerenes in the soot produced by flames. This thesis focuses on an experimental and modeling study of one of the many thermally metastable fullerenes. Specifically, this thesis establishes the true identity of one of the thermally metastable ftillerene produced in flames; the thesis investigates where in the flame the thermally metastable fullerene forms; the thesis reports thermochernical.
    [Show full text]
  • SOLUBILITY of FULLERENES C6o and C7 0 in WATER, D
    LPS XXVII 543 SOLUBILITY OF FULLERENES C6o AND C7 0 IN WATER, D. Heymann, Department of Geology and Geophysics, Rice University, Houston, TX 7725 7. e-mail: [email protected]. Fullerenes C60 and C70, the all-carbon molecules with closed-cage structures, have been found naturally in soot-rich clays and marls at the Cretaceous-Tertiary boundary [I].All were marine sediments which were permeated by water even after the consolidated rocks had become uplifted above sea level. Because of this, one would like to know the solubilities of C60 and C70 in water in order to evaluate how much of the fullerenes might have been leached from the sediments since their formation about 65 My ago. A direct measurement yielded essentially zero solubility. The solubilities of -C60 and C70 at 25 OC in seven normal alcohols obey the relationship InY = a + bX + cxZ, where Y is molefraction and X is the Hildebrand solubility parameter of the solvent. Extrapolation to the solubility parameter of water gave solubilities for C60 and C70 of 1.3~10-I and 1.3x10-~~ng/ml respectively with an uncertainty of one order of magnitude. Approximately 1 mg of C60 or C70 and about 5 ml of the alcohols were placed in screw-capped bottles. The bottles were stored for one month at 24.5 ? 0.5 OC, but were gently agitated twice every day which resulted in full equilibration. Also, 50 ml of water and fullerenes were stirred continuously in stoppered erlenmeyers for one month. Following filtration through 0.2 pm PTFE filters, the water was evaporated from the flask which was then rinsed repeatedly with a few ml HPLC toluene.
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2005/0136079 A1 Burangulov Et Al
    US 2005O136079A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0136079 A1 Burangulov et al. (43) Pub. Date: Jun. 23, 2005 (54) COSMETIC COMPOSITIONS CONTAINING Related U.S. Application Data FULLERENE CLUSTERS (60) Provisional application No. 60/475,203, filed on May (76) Inventors: Nail Burangulov, St. Petersburg (RU); 30, 2003. Alexander P. Moravsky, Tucson, AZ (US); Yuiya V. Kulikova, St. Publication Classification Petersburg (RU); George I. Dyachuk, St. Petersburg (RU); Raouf O. Loutfy, (51) Int. Cl." .......................... A61K 7/021; A61K 33/44 Tucson, AZ (US) (52) U.S. Cl. ............................. 424/401; 424/125; 424/63 Correspondence Address: SCULLY SCOTT MURPHY & PRESSER, PC (57) ABSTRACT 400 GARDEN CITY PLAZA SUTE 300 The present invention is directed to a cosmetic composition comprising effective amounts of fullerene clusters in asso GARDEN CITY, NY 11530 (US) ciation with cosmetically acceptable carrier to prevent or (21) Appl. No.: 10/858,361 retard free radical oxidation processes in the skin and to the method of using Said composition for reducing damage to (22) Filed: Jun. 1, 2004 healthy Skin or mucous membranes by free radicals. Patent Application Publication Jun. 23, 2005 Sheet 1 of 2 US 2005/0136079 A1 FIGURE 1 Patent Application Publication Jun. 23, 2005 Sheet 2 of 2 US 2005/0136079 A1 Product Raw Material FIGURE 2 US 2005/O136079 A1 Jun. 23, 2005 COSMETIC COMPOSITIONS CONTAINING pure Co and Co fullerenes, higher order-fullerenes, their FULLERENE CLUSTERS mixtures, crystalline Solvates of fullerenes with aromatic molecules, fullerenes adsorbed on graphite, etc. CROSS REFERENCE TO RELATED 0007. The high strength of the fullerene molecular crys APPLICATIONS tals results in their drastically different chemical and bio 0001.
    [Show full text]
  • Probing the Solubility of Selected Nanoscale Building Blocks
    PROBING THE SOLUBILITY OF SELECTED NANOSCALE BUILDING BLOCKS USING MOLECULAR SIMULATION By Patrick Scott Redmill Dissertation Submitted to the Faculty of the Graduate School of Vanderbilt University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOPSOPHY in Chemical Engineering December, 2008 Nashville, TN Approved: Peter T. Cummings Clare McCabe Scott Guelcher Eugene LeBoeuf M. Douglas LeVan To Mom and Dad SUPPORT LOCAL COLLEGE RADIO WRVU 91.1 FM ii ACKNOWLEDGEMENTS This work has been possible through the financial support of the National Science Foundation. Additionally, the simulations in this work were done using the computational resources at NERSC and ACCRE. I am grateful for the support, guidance, and patience I have received during my research from my advisors, Professor Peter T. Cummings and Clare McCabe. I would also like to thank the members of my Dissertation Committee for their time, valuable insights, and unique observations that they contributed to this work. Vanderbilt University, as a whole, deserves great thanks as well. I am very grateful for the exposure to some of the best educators in world that Vanderbilt provided. I truly consider Vanderbilt my academic home. I would like to thank Dr. Alberto Striolo, who was absolutely instrumental in initiating me to this work. Shannon Capps is also due special thanks for all of her hard work (i.e. things I didn’t want to do and passed off on a poor undergrad) while a student in the McCabe lab. Finally, I would like to thank my lab mates, in particular, Christina Payne, Peter Dyer, and Hugh Docherty.
    [Show full text]