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Sample records for carboranes

  1. Phosphazene Polymers Containing Carborane

    Science.gov (United States)

    Fewell, L. L.; Parker, J. A.; Basi, R. J.

    1986-01-01

    Addition of carborane increases thermal stability. Carborane-substituted polyphosphazenes prepared by thermal polymerization of phenylcarbonyl-pentachlorocyclotriphosphazene followed by reaction with sodium trifluoroethoxide to replace remaining chlorine atoms with trifluoroethoxy groups. Improved polymers offer high char yields and resistance to hydrolysis.

  2. Features of carborane-4 pyrolysis

    International Nuclear Information System (INIS)

    A phenomenological mathematical model, describing experiments on carborane disappearance and formation of condensate at 900-1700 K, was suggested. The concept of pyrolysis as interaction of electron-deficient carborane isomers and its derivatives was substantiated. The structure of electron-deficient isomer of carborane-4 was ascertained

  3. Carborane-containing liquid-crystalline polycrylates

    International Nuclear Information System (INIS)

    Carborane-containing homo- and copolyarylates were prepared by acceptor-catalytic polyesterification in solution from m-carboranedicarboxylic acid and 4,4'-dioxydiphenyl-o-carborane in combination with common dicarboxylic acids and bisphenols. The properties of the resulting polyarylates were studied, and the factors affecting the development of liquid-crystalline order in carborane-containing copolyarylates were discussed

  4. Development of carborane synthons: Synthesis and chemistry of (aminoalkyl)carboranes

    International Nuclear Information System (INIS)

    A number of (aminoalkyl)-1,2-closo-dodecaboranes have been synthesized to provide carboranes with a functional group for covalent incorporation into structures of potential use in the treatment of cancer by boron neutron capture therapy (BNCT). (Phthalimidoalkyl)acetylenes reacted with decaborane to give the corresponding carboranes; removal of the phthalimido group under mild conditions using sodium borohydride in 2-propanol furnished the (aminoalkyl)carboranes which were isolated as their hydrochloride salts. An alternative approach involved the conversion of an (iodoalkyl)- or a ((tosyloxy)alkyl)carborane to the azido derivative which gave the amine on hydrogenation. An effective way of attaching a carborane moiety to thiouracil, which is selectively taken up in melanoma cells, is illustrated by the acylation of two of these amines with thiouracil-5-carboxylic acid

  5. Sythesis and investigation of m-carborane-containing polybenzimidazoles

    International Nuclear Information System (INIS)

    New m-carborane-containing polybenzimidazoles (PBI) have been obtained by chemical cyclization of m-carborane-containing polyaminoamides (PAA) with the N-methyl-2-pyrrolidone-sulphuric anhydride complex or polyphosphoric acid esters being used as the cyclodehydrating reagents. The obtained m-carborane-containing PAA and PBI have been tested for solubility, heat resistance and chemical stability. The structure of m-carborane-containing PBI has been determined by abalysis of their infrared spectra

  6. Tetrabutylammonium fluoride promoted regiospecific reactions of trimethylsilyl-o-carborane with aldehydes

    International Nuclear Information System (INIS)

    Trimethylsilyl-o-carborane serves as o-carborane carbanion upon fluoride ion promoted reaction with carbonyl compounds. Thus, in the presence of tetrabutylammonium fluoride, trimethylsilyl-o-carborane undergoes facile, unprecedented, carbodesilylation with aromatic and aliphatic aldehydes. (author)

  7. Synthesis, radioiodination, and biodistribution of some nido- and closo-monocarbon carborane derivatives

    International Nuclear Information System (INIS)

    Iodination and radioiodination reactions of several anionic nido- and closo-monocarbon carboranes were conducted. Iodinations occurred more rapidly with nido-carboranes than with closo-carboranes. The most rapid iodination and radioiodination reactions occurred with unsubstituted carboranes. C-amino and C-ammonium derivatives did not iodinate under the conditions studied. Both nido- and closo-carboranes with C-NH-acetyl and C-NH-succinyl substituents iodinated, but the nido-carboranes iodinated under milder reaction conditions. Biodistributions of nido-1-succinylamido-[131I]carborane and closo-1-succinylamido-[125I]carborane were similar in mice, but blood clearance of the nido- compound was slower

  8. Carborane-based carbonic anhydrase inhibitors

    Czech Academy of Sciences Publication Activity Database

    Brynda, Jiří; Mader, Pavel; Šícha, Václav; Fábry, Milan; Poncová, Kristýna; Bakardjiev, Mario; Grüner, Bohumír; Cígler, Petr; Řezáčová, Pavlína

    2013-01-01

    Roč. 52, č. 51 (2013), s. 13760-13763. ISSN 1433-7851 R&D Projects: GA TA ČR(CZ) TE01020028; GA AV ČR IAAX00320901 Institutional support: RVO:68378050 ; RVO:61388963 ; RVO:61388980 Keywords : carbonic anhydrases * carboranes * drug discovery * inhibitors * structure elucidation Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 11.336, year: 2013

  9. Esters of o- and m-carborane-C-carboxylic acids with o- and m-C-carborane alcohols

    International Nuclear Information System (INIS)

    Acid chlorides of o- and m-carborane-C-carboxylic acids reacted with primary o- and m-C-carborane alcohols in anhydrous benzene to form in a high yield (81-86%) previously unknown corresponding o- and m-carborane-containing two- and three-nuclear esters. The composition and structure of the compounds prepared have been characterized by elementary analysis, 1H and 11B NMR, IR and UV spectroscopy, by measuring their molecular weights and melting points

  10. Transformations of isopropenyl-o-carborane and o-carborane at high pressures and temperatures

    International Nuclear Information System (INIS)

    By the methods of 1H and 13C of NMR-spectroscopy the reactivity of isopropenyl-o-carborane (1) and o-carborane (2) under the conditions of pressures up to 2500 MPa and temperatures up to 700 deg is studied. In the 1000-2500 MPa pressure and 350-400 deg temperature range the main product of thermal transformation 1 is dimer 2.5-di-(o-carborane-11-yl)-hexen-1. Isomerization of 2 in m-carborae which occurs under normal pressure and at 400 deg is totally suppressed at the pressure over 1000 MPa. At pressures of 1000-2500 MPa and temperatures over 500 deg in the presence of air 1 and 2 are polymerized with simultaneous boron atoms oxidation

  11. A stable α-chloroalkyllithium compound -2-lithiumchloromethyl-1-methyl-0-carborane

    International Nuclear Information System (INIS)

    2-Lithiumchloromethyl-1-methyl-0-carborane is obtained by the metallation of 2-chloromethyl-1-methyl-0-carborane with BunLi. Lithiumchloromethyl-0-carborane derivative reacts easily with CO2, PhCHO and H2O to form the corresponding acid, chlorohydrins and initial chloromethyl-1-methyl-2-0-carborane respectively. 2 refs

  12. Carborane-based inhibitors of carbonic anhydrases

    Czech Academy of Sciences Publication Activity Database

    Brynda, Jiří; Pachl, Petr; Šícha, Václav; Fábry, Milan; Grüner, Bohumír; Cígler, Petr; Řezáčová, Pavlína

    2015-01-01

    Roč. 22, č. 1 (2015), s. 3. ISSN 1211-5894. [Discussions in Structural Molecular Biology . Annual Meeting of the Czech Society for Structural Biology /13./. 19.03.2015-21.03.2015, Nové Hrady] R&D Projects: GA ČR GA15-05677S Institutional support: RVO:61388963 ; RVO:68378050 ; RVO:61388980 Keywords : carboranes * carbonic anhydrase Subject RIV: CE - Biochemistry

  13. Photoionization and fragmentation of closo-carboranes

    Energy Technology Data Exchange (ETDEWEB)

    Riehs, Norman Frank; Jochims, Hans-Werner; Serdaroglu, Ertugrul; Ruehl, Eckart [Physikalische und Theoretische Chemie, Freie Universitaet Berlin, Takustr. 3, 14195 Berlin (Germany); Dowben, Peter A. [Department of Physics and Astronomy, University of Nebraska-Lincoln, NE 68588-0111 (United States)

    2008-07-01

    Photoionization and photon-induced fragmentation of isomeric icosahedral closo-carboranes by monochromatic synchrotron radiation is reported. Vacuum ultraviolet radiation from the 3 m NIM-I beam line at the storage ring BESSY (Berlin) was used for the experiments. This allows us to measure ionization thresholds and fragmentation patterns at various photon energies. In spite of complexities that result because of the natural isotope abundance of boron and photon-induced loss of hydrogen, the distinct mass spectrometry fragmentation patterns have been partially identified. At low photoionization energies, we find that the loss of atomic hydrogen corresponds to even numbers of hydrogen atoms. Distinct differences between the isomers of closo-dicarbadodecaborane (orthocarborane (1,2-C{sub 2}B{sub 10}H{sub 12}), metacarborane (1,7-C{sub 2}B{sub 10}H{sub 12})), paracarborane (1,12-C{sub 2}B{sub 10}H{sub 12}) are observed indicating that the loss of pairs of hydrogen depends on the carbon placement within the carborane cage. Furthermore, fragmentation of the cage into singly charged fragments of variable mass is observed along with stable doubly charged intact carborane cages. These results are discussed along with plausible fragmentation mechanisms.

  14. Triflyloxy-substituted carboranes as useful weakly coordinating anions.

    Science.gov (United States)

    Press, Loren P; McCulloch, Billy J; Gu, Weixing; Chen, Chun-Hsing; Foxman, Bruce M; Ozerov, Oleg V

    2015-09-25

    New carborane anions carrying one or three triflyloxy substituents are described. The mono-triflyloxy substituted carborane can be halogenated to give pentabromo and decachloro derivatives with preservation of the B-OTf linkage. The use of [HCB11Cl10OTf](-) as a weakly coordinating anion is demonstrated. PMID:26251850

  15. Intriguing emission properties of triphenylamine-carborane systems.

    Science.gov (United States)

    Kim, So-Yoen; Cho, Yang-Jin; Jin, Guo Fan; Han, Won-Sik; Son, Ho-Jin; Cho, Dae Won; Kang, Sang Ook

    2015-06-28

    Electron donor-acceptor (D-A) systems with a triphenylamino moiety (D) and ortho-carborane (A) show three kinds of intriguing emissions that can be attributed to the local excited state, the intramolecular charge-transfer state, and the aggregation-induced emission state. The emission behaviors depend on which positions of the carborane are substituted. PMID:26013604

  16. Closo-Carborane-metal complexes containing metal-carbon and metal-boron sigma-bonds

    International Nuclear Information System (INIS)

    This paper examines the metal derivatives of the closo-carboranes formed through carborane carbon-metal and carborane boron-metal bonds. In order to provide a better perspective of the closo-carborane-metal compounds the authors include derivatives containing carboranyl groups bonded to boron and silicon, which are normally classified as nonmetals. The structures, nomenclature system, and general preparative methods of the closo-carboranes are examined

  17. Iridium Cyclometalates with Tethered o-Carboranes: Impact of Restricted Rotation of o-Carborane on Phosphorescence Efficiency.

    Science.gov (United States)

    Lee, Young Hoon; Park, Jihyun; Lee, Junseong; Lee, Sang Uck; Lee, Min Hyung

    2015-07-01

    Iridium(III) cyclometalates (1c and 2c) in which the two carborane units on the 4- or 5-positions of 2-phenylpyridine (ppy) ligands were tethered by an alkylene linker were prepared to investigate the effect of free rotation of o-carborane on phosphorescence efficiency. In comparison with the unlinked complex, tethering the o-carboranes to the 5-positions of ppy ligands (2c) enhanced phosphorescence efficiency by over 30-fold in polar medium (Φ(PL) = 0.37 vs 0.011 in THF), while restricting the rotation of o-carborane at the 4-positions (1c) negatively affected the phosphorescence efficiency. The different effects of restricted rotation of o-carborane on phosphorescence efficiency were likely a result of the different variations of the carboranyl C-C bond distances in the excited state. PMID:26075816

  18. First boronization in KSTAR: Experiences on carborane

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Suk-Ho, E-mail: sukhhong@nfri.re.kr [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Lee, Kun-Su; Kim, Kwang-Pyo; Kim, Kyung-Min; Kim, Hong-Tack [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Sun, Jong-Ho; Woo, Hyun-Jong [Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Department of Electrical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Park, Jae-Min [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Park, Eun-Kyong [Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Department of Electrical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Kim, Woong-Chae; Kim, Hak-Kun; Park, Kap-Rai; Yang, Hyung-Lyeol; Oh, Yeong-Kook; Na, Hoon-Kyun [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Lho, Taehyeop [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Chung, Kyu-Sun [Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Department of Electrical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2011-08-01

    First boronization was performed in KSTAR tokamak during 2009 campaign in order to reduce oxygen impurities and to lower the power loss due to radiation. We report the results from the experiences on carborane during the first boronization in KSTAR. After the boronization, H{sub 2}O and O{sub 2} level in the vacuum vessel are reduced significantly. The characteristics of the deposited thin films were analyzed by variable angle spectroscopic ellipsometry, XPS, and AES. {approx}1.78 x 10{sup 16} cm{sup -2} s{sup -1} of carbon flux on the wall is estimated by using cavity technique.

  19. Research advancements and applications of carboranes in nuclear medicinal chemistry

    International Nuclear Information System (INIS)

    Because of their uniquely high thermal and chemical stabilities, carboranes have become a subject of study with high interest in the chemistry of supra molecules, catalysts and radiopharmaceuticals. In recent years, the role of carboranes in nuclear medicinal chemistry has been diversified, from the traditional use in boron neutron capture therapy (BNCT), to the clinical applications in molecular radio imaging and therapy. This paper provides an overview of the synthesis and characterization of carboranes and their applications in nuclear medicinal chemistry, with highlights of recent key advancements in the re- search areas of BNCT and radio imaging. (authors)

  20. Reactivity of carborane-4 in the water vapor medium

    International Nuclear Information System (INIS)

    Reactivity of carborane-4 with respect to water vapor was investigated with the use of shock tubes and fast compression plant. Reculiarities of interaction of mentioned components in the mixture 0.056C-2B4H6+0.444H2O+0.5Ar were determined. It was established that carborane reacted intensively with water vapor at temperatures above 1300 K, its reactivity at that exceeded one of hydrogen in the air. Chemical activity of carborane in water vapor medium decreased almost by two orders with decrease of temperature from 1000 to 900 K

  1. Regularities of ignition in the system of carborane-4-water vapor

    International Nuclear Information System (INIS)

    A study was made on kinetics of condensed phase formation in carboran-argon and carborane-water vapor-argon systems at 920-1020 K temperature, and 0.1 mPa pressure. It was revealed, that carborane pyrolysis products were subjected to oxidation by water vapor, and carborant itself didn't react with water vapor. Correlation of time characteristics of carborane pyrolysis and ignition in carborane-water vapor system in 900-1600 K range was conducted. It is shown that at T> 1000 K the ignition takes place at the stage of carborane pyrolysis, and at T<1000 K -after its termination

  2. Boronization of Russian tokamaks from carborane precursors

    International Nuclear Information System (INIS)

    A new and cheap boronization technique using the nontoxic and nonexplosive solid substance carborane has been developed and successfully applied to the Russian tokamaks T-11M, T-3M, T-10 and TUMAN-3. The glow discharge in a mixture of He and carborane vapor produced the amorphous B/C coating with the B/C ratio varied from 2.0-3.7. The deposition rate was about 150 nm/h. The primary effect of boronization was a significant reduction of the impurity influx and the plasma impurity contamination, a sharp decrease of the plasma radiated power, and a decrease of the effective charge. Boronization strongly suppressed the impurity influx caused by additional plasma heating. ECR- and ICR-heating as well as ECR current drive were more effective in boronized vessels. Boronization resulted in a significant extension of the Ne- and q-region of stable tokamak operation. The density limit rose strongly. In Ohmic H-mode energy confinement time increased significantly (by a factor of 2) after boronization. It rose linearly with plasma current Ip and was 10 times higher than Neo-Alcator time at maximum current. ((orig.))

  3. Fluorinated and trifluoromethylated CB11 carborane anions and radicals

    Czech Academy of Sciences Publication Activity Database

    Higelin, Alexander; Šembera, Filip; Tamadon, F.; Wahab, Abdul; Janoušek, Zbyněk; Ludvík, Jiří; Klíma, Jiří; Crespo, R.; Piqueras, M. C.; Michl, Josef

    San Francisco: American Chemical Society, 2014. 37FLUO. [ACS National Meeting & Exposition /248./. 10.08.2014-14.08.2014, San Francisco] Institutional support: RVO:61388963 Keywords : carborane anions Subject RIV: CC - Organic Chemistry

  4. Synthesis and thermal stability of carborane-containing phosphazenes

    Science.gov (United States)

    Fewell, L. L.; Parker, J. A.; Basi, R. J.

    1983-01-01

    Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034

  5. Synthesis and thermal stability of carborane containing phosphazenes

    Science.gov (United States)

    Fewell, L. L.; Basi, R. J.; Parker, J. A.

    1983-01-01

    Carborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring chain equilibrium processes of decomposition.

  6. Synthesis and characterization of nido-carborane-cobalamin conjugates

    Energy Technology Data Exchange (ETDEWEB)

    Hogenkamp, Harry P.C. E-mail: hogen001@tc.umn.edu; Collins, Douglas A.; Live, David; Benson, Linda M.; Naylor, Stephen

    2000-01-01

    Three vitamin B{sub 12} (cyanocobalamin) conjugates bearing one nido-carborane molecule or two nido-carborane molecules linked to the propionamide side chains via a four carbon linker have been synthesized. Reaction of o-carboranoylchloride with 1,4-diaminobutane in pyridine produced nido-carboranoyl(4-amidobutyl)amine, which was linked to the b- and d-monocarboxylic acids and the b,d-dicarboxylic acid of cyanocobalamin. Mass spectrometry analysis as well as {sup 11}B nuclear magnetic resonance demonstrated that during the reaction of o-carboranonylchloride with diaminobutane one of the boron atoms was eliminated. In vitro biological activity of the cyanocobalamin-nido-carborane conjugates was assessed by the unsaturated vitamin B{sub 12} binding capacity assay. When compared with {sup 57}Co cyanocobalamin, the biological activity of cyanocobalamin-b-nido-carborane, cyanocobalamin-d-nido-carborane, and cyanocobalamin-b-d-bis-nido-carborane conjugates were 92.93%, 35.75%, and 37.02%, respectively. These findings suggest that the {sup 10}B cobalamin conjugates might be useful agents in treating malignant tumors via neutron capture therapy.

  7. Synthesis and characterization of nido-carborane-cobalamin conjugates

    International Nuclear Information System (INIS)

    Three vitamin B12 (cyanocobalamin) conjugates bearing one nido-carborane molecule or two nido-carborane molecules linked to the propionamide side chains via a four carbon linker have been synthesized. Reaction of o-carboranoylchloride with 1,4-diaminobutane in pyridine produced nido-carboranoyl(4-amidobutyl)amine, which was linked to the b- and d-monocarboxylic acids and the b,d-dicarboxylic acid of cyanocobalamin. Mass spectrometry analysis as well as 11B nuclear magnetic resonance demonstrated that during the reaction of o-carboranonylchloride with diaminobutane one of the boron atoms was eliminated. In vitro biological activity of the cyanocobalamin-nido-carborane conjugates was assessed by the unsaturated vitamin B12 binding capacity assay. When compared with 57Co cyanocobalamin, the biological activity of cyanocobalamin-b-nido-carborane, cyanocobalamin-d-nido-carborane, and cyanocobalamin-b-d-bis-nido-carborane conjugates were 92.93%, 35.75%, and 37.02%, respectively. These findings suggest that the 10B cobalamin conjugates might be useful agents in treating malignant tumors via neutron capture therapy

  8. The study of the Suzuki cross-combination reaction in a carborane series

    International Nuclear Information System (INIS)

    Products of the Suzuki cross-combination reaction of 9-iodine-m-carborane and 9-iodine-o-carborane with phenylboric acid and with dibutyl ester of vinylboric acid catalyzed by diverse palladium compounds have been studied. It has been ascertained that in carborane series the reaction proceeds in some other way than with organic halogen compounds

  9. Regularities of ignition of carborane-4 in oxygen-containing media

    International Nuclear Information System (INIS)

    Ignition of carborane-4-oxygen-argon mixtures behind reflected waves in a strike tube at 700-1600 k and 0.05-0.15 MPa has been studied experimentally. The calculation of initial products of carborane oxidation was made using semiempirical MNDO quantum-chemical method. Kinetic scheme of the initial stage of carborane oxidation is suggested. Refs. 17, figs. 3

  10. Thermal transformations of O,O-diethyl-S(o-carborane-9-yl)thiophosphite

    International Nuclear Information System (INIS)

    Thermal transformations of 0,0-diethyl-S-(o-carborane-9-yl)thiophosphite have been studied. Thermolysis of the compound at 120 deg C gives rise to formation of a mixture of substances, among which O-ethyl-S,S-bis(o-carborane-9-yl) dithiophosphite, O-ethyl-S,S-bis(o-carborane-9-yl)dithiophosphate, O,O-diethyl-S-(carborane-9-yl)thiophosphate, O-ethyl-S-(-carborane-0-yl)ethylthiophosphonate and diethylphosphite have been discovered. The conclusion on homolytic character of the processes occurring during thermolysis is made

  11. Facial Synthesis of o-Carborane-Substituted Alkenes and Allenes by a Regioselective Ene Reaction of 1,3-Dehydro-o-carborane.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2015-07-13

    1,3-Dehydro-o-carborane is a useful synthon for selective cage boron functionalization of o-carboranes. It reacts readily with alkenes or alkynes to give a variety of cage B(3)-alkenyl/allenyl o-carboranes by ene reactions in very high yields and excellent regioselectivity. This can be ascribed to the highly polarized cage C-B multiple bond, which lowers the activation barriers of the ene reaction. PMID:26074122

  12. N,O-Type Carborane-Based Materials

    Directory of Open Access Journals (Sweden)

    José Giner Planas

    2016-05-01

    Full Text Available This review summarizes the synthesis and coordination chemistry of a series of carboranyl ligands containing N,O donors. Such carborane-based ligands are scarcely reported in the literature when compared to other heteroatom-containing donors. The synthetic routes for metal complexes of these N,O-type carborane ligands are summarized and the properties of such complexes are described in detail. Particular attention is paid to the effect that the incorporation of carboranes has into the coordination chemistry of the otherwise carbon-based ligands and the properties of such materials. The reported complexes show a variety of properties such as those used in magnetic, chiroptical, nonlinear optical, catalytic and biomedical applications.

  13. Carborane compounds for neutron capture therapy of malignant melanoma

    International Nuclear Information System (INIS)

    The possibility of using thiouracil as a vehicle for stable nuclei such as 10B for neutron capture therapy (NCT) of melanoma was first discussed by Fairchild and co-workers in 1982. The author's research has been directed towards the design and synthesis of a number of o-carboranyl-thiouracils, the ten boron atoms of the carborane cage having a clear advantage for NCT. The first step was the preparation, previously reported, of thiouracils bearing an alkyl group continuing a triple bond for later elaboration to a carborane. The present paper describes the continuation of this work with the preparation of the carboranes of this series and its extension to the synthesis of a thiouracil in which a carboranylalkyl group is attached to the nitrogen in the 3-position

  14. Design of Carborane Molecular Architectures via Electronic Structure Computations

    Directory of Open Access Journals (Sweden)

    Josep M. Oliva

    2009-01-01

    Full Text Available Quantum-mechanical electronic structure computations were employed to explore initial steps towards a comprehensive design of polycarborane architectures through assembly of molecular units. Aspects considered were (i the striking modification of geometrical parameters through substitution, (ii endohedral carboranes and proposed ejection mechanisms for energy/ion/atom/energy storage/transport, (iii the excited state character in single and dimeric molecular units, and (iv higher architectural constructs. A goal of this work is to find optimal architectures where atom/ion/energy/spin transport within carborane superclusters is feasible in order to modernize and improve future photoenergy processes.

  15. Novel carborane based inhibitors of carbonic anhydrase IX

    Czech Academy of Sciences Publication Activity Database

    Štěpánková, J.; Řezáčová, Pavlína; Brynda, Jiří; Harvanová, M.; Mašek, V.; Nová, A.; Siller, M.; Das, V.; Doležal, D.; Grüner, Bohumír; Šícha, Václav; Konečný, P.; Znojek, P.; Džubák, P.; Hajdúch, M.

    2015-01-01

    Roč. 75, 15 Suppl (2015), s. 4492. ISSN 0008-5472. [Annual Meeting of the American Association for Cancer Research (AACR) /106./. 18.04.2015-22.04.2015, Philadelphia] Institutional support: RVO:61388963 ; RVO:61388980 Keywords : carbonic anhydrase * carborane based inhibitors Subject RIV: CE - Biochemistry

  16. Polymers containing borane or carborane cage compounds and related applications

    Science.gov (United States)

    Bowen, III, Daniel E.; Eastwood, Eric A.

    2012-06-05

    Polymers comprising residues of borane and/or carborane cage compound monomers having at least one polyalkoxy silyl substituent. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Methods of making and applications for using such polymers are also disclosed.

  17. Compositions containing borane or carborane cage compounds and related applications

    Science.gov (United States)

    Bowen, III, Daniel E; Eastwood, Eric A

    2013-05-28

    Compositions comprising a polymer-containing matrix and a filler comprising a cage compound selected from borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer. Methods of making and applications for using such compositions are also disclosed.

  18. Compositions containing borane or carborane cage compounds and related applications

    Energy Technology Data Exchange (ETDEWEB)

    Bowen, III, Daniel E; Eastwood, Eric A

    2014-11-11

    Compositions comprising a polymer-containing matrix and a filler comprising a cage compound selected from borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer. Methods of making and applications for using such compositions are also disclosed.

  19. Compositions containing borane or carborane cage compounds and related applications

    Energy Technology Data Exchange (ETDEWEB)

    Bowen, III, Daniel E.; Eastwood, Eric A.

    2015-09-15

    Compositions comprising a polymer-containing matrix and a filler comprising a cage compound selected from borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer. Methods of making and applications for using such compositions are also disclosed.

  20. Synthesis of 9-pentacarbonylrhenium-m-carborane from 9-m-carboranecarboxylic acid chloroanhydride

    International Nuclear Information System (INIS)

    By interaction of chloroanhydrides of 9-o- and 9-m-carboranecarboxylic acids with NaRe(CO)5 ortho-(1) and meta-(2) derivatives of σ-(carborane-9-carbonyl) rhenium pentacarbonyl are produced in tetrahydrofuran at -70 deg C. With thermal decarbonization in heptane complex 1 is decomposed to 0-carborane, Re2(CO)10 and CO, and complex 2 forms 9-pentacarbonylrhenium-m-carborane

  1. Carborane Derivatives for Nuclide Therapy and Imaging : Synthesis and Radio-labelling

    OpenAIRE

    Winberg, Karl Johan

    2003-01-01

    This thesis describes synthesis and radiohalogenation of closo-carborane and nido-carborate derivatives for application in nuclide therapy and imaging. The work could be divided in to four sections. In the first section, the synthesis of three boronated DNA-intercalators – 1–(N-9-acridinyl-3-aminopropyl)-para-carborane-12-carboxylic acid hydrogen chloride, 1-[1-(N-9-acridinyl-3-aminopropyl)-para-carborane 12-(3-propyloxi)]-1,3-propanediol, 1-(N-9-acridinyl-3-amino-propyl)-1-ortho-carborane-2-...

  2. On the influence of dibenzyl-o-carborane on radiation-induced aging of polymethylmethacrylate

    International Nuclear Information System (INIS)

    Influence of dibenzyl-o-carborane additions in radiation resistance of polymethylmethacrylate (PMMA) subjected to gamma irradiation (60Co) by doses from 0 to 8.0 Mrad at dose rate of 0.7 Mrad/h was studied. It was ascertained that carborane manifests radioprotective properties during radiation-induced aging of PMMA prepared in its presence, it also inhibits thermal decomposition of the irradiated polymer. Influence of gamma radiation on PMMA, containing carborane additions as mechanical impurities, results in increase in the polymer thermal resistance, very likely at the expense of interaction between oxygen-containing groups of macromolecules and addition carborane fragments

  3. Chemical transformations during heating of carborane-containing resols and resites

    International Nuclear Information System (INIS)

    Chemical transformations were studied during the heating of resols containing carborane and corresponding resites. It was found that in the temperature range 50-2000, structure formation of oligomers containing carborane takes place by a mechanism which is conventional for resols. At temperatures higher than 2000 significant chemical transformations of carborane groups of resites take place, the degree of transformations depending on conditions of heating (air, vacuum). It was shown that the most considerable differences in thermal stability of conventional phenol-formalhyde and carborane-containing resites are observed under conditions of thermal oxidizing breakdown. Thermal oxidizing breakdown of several model compounds was studied

  4. The interaction of the carborane-containing electrophiles with triethyl phosphate. Synthesis of the novel phosphates containing carboranyl group

    International Nuclear Information System (INIS)

    The interaction of o-carborane-1-yl mesylates with triethyl phosphite and sodium diethyl phosphite are studied. Synthesis of novel carborane-containing phosphonates has been effected. Reaction of o-carboranylacetyl chloride with triethyl phosphite is shown to lead to O,O-diethyl(E)-2-(o-carborane-1-yl)-1-(o-carborane-1-ylacetoxy)vinyl phosphonate rather than to ketophosphonate

  5. Icosahedral metallacarborane/carborane species derived from 1,1'-bis(o-carborane).

    Science.gov (United States)

    Thiripuranathar, Gobika; Man, Wing Y; Palmero, Cesar; Chan, Antony P Y; Leube, Bernhard T; Ellis, David; McKay, David; Macgregor, Stuart A; Jourdan, Laure; Rosair, Georgina M; Welch, Alan J

    2015-03-28

    Examples of singly-metallated derivatives of 1,1'-bis(o-carborane) have been prepared and spectroscopically and structurally characterised. Metallation of [7-(1'-1',2'-closo-C2B10H11)-7,8-nido-C2B9H10](2-) with a {Ru(p-cymene)}(2+) fragment affords both the unisomerised species [1-(1'-1',2'-closo-C2B10H11)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (2) and the isomerised [8-(1'-1',2'-closo-C2B10H11)-2-(p-cymene)-2,1,8-closo-RuC2B9H10] (3), and 2 is easily transformed into 3 with mild heating. Metallation with a preformed {CoCp}(2+) fragment also affords a 3,1,2-MC2B9-1',2'-C2B10 product [1-(1'-1',2'-closo-C2B10H11)-3-Cp-3,1,2-closo-CoC2B9H10] (4), but if CoCl2/NaCp is used followed by oxidation the result is the 2,1,8-CoC2B9-1',2'-C2B10 species [8-(1'-1',2'-closo-C2B10H11)-2-Cp-2,1,8-closo-CoC2B9H10] (5). Compound 4 does not convert into 5 in refluxing toluene, but does do so if it is reduced and then reoxidised, perhaps highlighting the importance of the basicity of the metal fragment in the isomerisation of metallacarboranes. A computational study of 1,1'-bis(o-carborane) is in excellent agreement with a recently-determined precise crystallographic study and establishes that the {1',2'-closo-C2B10H11} fragment is electron-withdrawing compared to H. PMID:25702632

  6. Polymers containing borane or carborane cage compounds and related applications

    Energy Technology Data Exchange (ETDEWEB)

    Bowen, III, Daniel E; Eastwood, Eric A

    2013-04-23

    Polymers comprising residues of cage compound monomers having at least one polyalkoxy silyl substituent are provided. The cage compound monomers are selected from borane cage compound monomers comprising at least 7 cage atoms and/or carborane cage compound monomers comprising 7 to 11 cage compound monomers. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Articles of manufacture comprising such polymers are also disclosed.

  7. o-Carborane-based anthracene: a variety of emission behaviors.

    Science.gov (United States)

    Naito, Hirofumi; Morisaki, Yasuhiro; Chujo, Yoshiki

    2015-04-20

    An o-carborane-based anthracene was synthesized, and single crystals, with incorporated solvent molecules, were obtained from the CHCl3 , CH2 Cl2 , and C6 H6 solutions. The anthracene ring in the crystal is highly distorted by the formation of a π-stacked dimer between the anthracene units. The crystals exhibited a variety of emission behaviors such as aggregation-induced emission (AIE), crystallization-induced emission (CIE), aggregation-caused quenching (ACQ), and multichromism. PMID:25729004

  8. Synthesis of unsymmetrical N-carboranyl NHCs: directing effect of the carborane anion.

    Science.gov (United States)

    Asay, Matthew J; Fisher, Steven P; Lee, Sarah E; Tham, Fook S; Borchardt, Dan; Lavallo, Vincent

    2015-03-28

    The syntheses of unsymmetrical N-heterocyclic carbenes (NHCs) that contain a single N-bound icosahedral carborane anion substituent are reported. Both anionic C-2 and doubly deprotonated dianionic C-2/C-5 NHC lithium complexes are isolated. The latter species is formed selectively, which reveals a surprising directing effect conveyed by icosahedral carborane anion substituents. PMID:25387660

  9. Carborane phosphorus-derivatives as ligands for Pd-catalyzed cross-coupling reactions

    International Nuclear Information System (INIS)

    Synthesis of carborane-containing phosphine ligands possessing different steric and electronic properties has been considered. Testing of the given ligands in Pd-catalyzed Suzuki-Miyaura reaction demonstrated that sterically volume phosphine ligands with acceptor carborane substitutes possessed the most catalytic activity

  10. Altering the inclusion properties of CTV through crystal engineering: CTV, carborane, and DMF supramolecular assemblies

    Science.gov (United States)

    Hardie; Raston; Wells

    2000-09-01

    The complexes [Na(CTV)2(OH)(H2O)](H2O)(DMF)2(o-carborane) (3; CTV = cyclotriveratrylene), [K(OH)(CTV)(DMF)]2(o-carborane) (4), [(DMF)(CTV)]2(H2O)4(o-carborane) (5), and (o-carborane)(CTV)(DMF)2 (6) all form as crystalline inclusion complexes from N,N'-dimethylformamide (DMF) solution. Complexes 3 and 4 are the first reported examples of CTV acting as a chelating ligand, with two CTV molecules coordinating cis to the six-coordinate M+ centers (M=Na, K). The extended structures of complexes 3-5 are similar, forming extended coordinate and/or hydrogen-bonding interactions and all feature intracavity complexation of DMF by CTV, while the complex 6 forms an assembly of (o-carborane) intersection of two sets (CTV) ball-and-socket supermolecules with DMF as a channel-type included guest. PMID:11003008

  11. Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB4H6C - units. Crown carboranes

    International Nuclear Information System (INIS)

    The open-chain dialkynes EtC≡C(CH2)nC≡CEt (n = 4, 6), the trialkyne HC≡C(CH2)5C≡CH, and the cyclic dialkynes CH2(CH2)4C≡C(CH2)nC≡C (n = 4-6) were treated with B5H9 and (C2H5)3 to give the corresponding nido-carborane oligomers, in which the original -C≡C- units are converted to -CB4H6C- nido-carborane cages. In each case, all available -C≡C- groups were transformed to carborane moieties. No partially converted products (having both carborane and -C≡C- groups in the chain) were found; when the B5H9/-C≡C- ratio employed was 2+ and oxidative fusion, forming products incorporating C4B8 cages. The cyclic bis(carborane) CH2(CH2)4CB4H6C(CH2)5CB4H6C is an air-stable oil that can be deprotonated but does not under metal-promoted oxidative fusion. All products were characterized by 11B and 1H NMR, infrared, visible-uv, and mass spectroscopy, and the 13C NMR spectra of linear bis(carboranes) are reported. 9 references, 7 figures, 4 tables

  12. Metalation of carborane phosphines and arsines by Rh(1) and Ir(1) complexes

    International Nuclear Information System (INIS)

    Consideration is being given to results of investigation on using reactions of cyclometallation by Rh(1) and Ir(1) complexes in the series of carborane phosphines and arsines for preparation of five-membered exocyclic compounds, containing B-M σ-bond. Stereochemical composition of cyclometallated carborane complexes of rhodium and iridium has been established on the basis of the data on 1H, 31P and 11B NMR spectroscopy. It is shown that boron atoms of o-carborane nucleus, being in 3(6)-position, are subjected to metallation

  13. Synthesis of bidentate o-carborane-containing phosphine and arsine ligands and preparation of their complexes with chromium-, molybdenum-, tungsten-, iron- and nickel carbonyls

    International Nuclear Information System (INIS)

    A number of bidentate o-carborane phosphine and arsine ligands have been synthesized and their chelate complexes with carbonyls of chromium, molybdenum, tungsten, iron and nickel are obtained. 1-mercapto-2-dimethylarsnomethyl-o-carborane and 1-mercapto-2-diethylaminomethyl-o-carborane with molybdenum and tungsten carbonyls provide substitution products of only one CO group. 1-diphenylphosphino-2-diphenylphosphinomethyl-o-carborane and 1,2-bis(diphenylphosphinomethyl)-o-carborane form complexes with NiCl2. Simplicity of complex formation of bidentate carborane ligands with group 6 metal carbonyls increases in the series Cr(CO)6 6 6

  14. Cage Opening of a Carborane Ligand by Metal Cluster Complexes.

    Science.gov (United States)

    Adams, Richard D; Kiprotich, Joseph; Peryshkov, Dmitry V; Wong, Yuen Onn

    2016-05-01

    The reaction of Os3 (CO)10 (NCMe)2 with closo-o-C2 B10 H10 has yielded two interconvertible isomers Os3 (CO)9 (μ3 -4,5,9-C2 B10 H8 )(μ-H)2 (1 a) and Os3 (CO)9 (μ3 -3,4,8-C2 B10 H8 )(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2 B10 H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3 (CO)9 (μ-H)2 (μ3 -4,5,9-μ3 -7,11,12-C2 B10 H7 )Os3 (CO)9 (μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3 (CO)9 (μ-H)(μ3 -3,4,8-μ3 -7,11,12-C2 B10 H8 )Os3 (CO)9 (μ-H) (3) by a novel opening of the carborane cage with loss of H2 . PMID:26971388

  15. Nickel-catalyzed cross-coupling reactions of o-carboranyl with aryl iodides: facile synthesis of 1-aryl-o-carboranes and 1,2-diaryl-o-carboranes.

    Science.gov (United States)

    Tang, Cen; Xie, Zuowei

    2015-06-22

    A nickel-catalyzed arylation at the carbon center of o-carborane cages has been developed, thus leading to the preparation of a series of 1-aryl-o-carboranes and 1,2-diaryl-o-carboranes in high yields upon isolation. This method represents the first example of transition metal catalyzed C,C'-diarylation by cross-coupling reactions of o-carboranyl with aryl iodides. PMID:25959849

  16. Synthesis of mono-, di-, tri-, and tetraethyl-o-carboranes by electrophilic alkylation of o-carborane with ethyl bromide in the presence of AlCl3 and their transformations

    International Nuclear Information System (INIS)

    Optimal conditions for preparation of 9-ethyl-, 9,12-diethyl, 8,9,12-triethyl- and 8,9,10,12-tetraethyl-o-carboranes under the action of EtBr on o-carborane in the presence of AlCl3 were determined. The behavior of these o-carborane derivatives with respect to electrophilic and nucleophilic reagents was studied. 17 refs.; 3 tabs

  17. Carborane-containing urea-based inhibitors of glutamate carboxypeptidase II: Synthesis and structural characterization.

    Science.gov (United States)

    Youn, Sihyun; Kim, Kyung Im; Ptacek, Jakub; Ok, Kiwon; Novakova, Zora; Kim, YunHye; Koo, JaeHyung; Barinka, Cyril; Byun, Youngjoo

    2015-11-15

    Glutamate carboxypeptidase II (GCPII) is a zinc metalloprotease on the surface of astrocytes which cleaves N-acetylaspartylglutamate to release N-acetylaspartate and glutamate. GCPII inhibitors can decrease glutamate concentration and play a protective role against apoptosis or degradation of brain neurons. Herein, we report the synthesis and structural analysis of novel carborane-based GCPII inhibitors. We determined the X-ray crystal structure of GCPII in complex with a carborane-containing inhibitor at 1.79Å resolution. The X-ray analysis revealed that the bulky closo-carborane cluster is located in the spacious entrance funnel region of GCPII, indicating that the carborane cluster can be further structurally modified to identify promising lead structures of novel GCPII inhibitors. PMID:26459214

  18. Carborane Anions: As Weakly Coordinating Counterions and Coordinating Ligands for Catalyst Design

    OpenAIRE

    Wright, James Henry

    2013-01-01

    1-carba-closo-dodecaborates, more commonly referred to as carborane anions, are icosahedral CB11 cages with substituents at each vertex. These substituents are highly variable allowing for a large range of properties. Such properties include being weakly basic, chemically inert, non-nucleophilic, and resistant to reduction or oxidation. Due to these properties, carborane anions have been given the term "weakly coordinating" to describe their interactions with cations. The isolation of numerou...

  19. Alkynyl substituted carboranes as precursors to boron carbide thin films, fibers and composites

    International Nuclear Information System (INIS)

    In this paper the use of alkynyl substituted derivatives of o-carborane as precursors to boron containing ceramics is described. These compounds undergo a thermally or photochemically induced polymerization to afford cross linked polyakynyl-o-carborane derivatives. The increase in molecular weight should allow for increased Tg's and the retention of modelled polymer preforms. In this report, these modification reactions are described. In addition, the retention of molded polymer preforms were analyzed after UV exposure and inert atmosphere pyrolysis

  20. Labelled compounds of interest as antitumour agents. Pt. 4: Deuteration and tritiation of a nitroimidazole-carborane designed for BNCT

    International Nuclear Information System (INIS)

    Quenching the anion generated from a 2-(ω-carboranylalkyl)dithiane with 2H2O at -78oC and at 0oC introduced deuterium exclusively at C-2 of the carborane. Extension of this model reaction to a bioreductively-targetted carborane allowed the synthesis of 2-[2H]- and 2-[3H]-isotopomers of a nitroimidazole-carborane which is of interest in boron neutron capture therapy (BNCT) of cancer. (author)

  1. The direct imaging and observed packing behaviour of othro-carborane molecules within single walled carbon nanotubes

    International Nuclear Information System (INIS)

    Ortho-carborane molecules have been inserted into single walled carbon nanotubes (SWNTs) and imaged directly by high resolution transmission electron microscopy (HRTEM). Direct imaging revealed that both discrete molecules and zig-zag 1D chains of o-carborane molecules were observed to pack into SWNT capillaries. Upon further e-beam irradiation, partial decomposition and rearrangement of clusters of o-carborane molecules was observed

  2. Inductive effects of 10 and 12-vertex closo-carborane anions: cluster size and charge make a difference.

    Science.gov (United States)

    Estrada, Jess; Lugo, Christopher A; McArthur, Scott G; Lavallo, Vincent

    2016-01-31

    A phosphine containing a 10-vertex carborane anion substituent and its subsequent ligation to a Rh(I) carbonyl complex is reported. The complex is characterized by NMR spectroscopy and a single crystal X-ray diffraction study. In addition, the inductive effects of both 10 and 12 vertex C-functionalized closo-carborane anions are elucidated via I.R. analysis of the CO stretching frequencies of two Rh carbonyl complexes. Unlike C-functionalized neutral o-carborane the 10 and 12-vertex carborane anions are both strong electron donor substituents. PMID:26671630

  3. Optical characteristic analysis of the boronization process by using carborane

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Wonwook; Park, Kyungdeuk; Choi, Youngsun; Oh, Chahwan [Hanyang University, Seoul (Korea, Republic of)

    2014-09-15

    Boronization with carborane (C{sub 2}B{sub 10}H{sub 12}) was achieved in a vacuum vessel coupled to a filament discharge system. Optical emission spectroscopy was employed to characterize the boronization process. The Balmer lines of hydrogen and deuterium were measured, and the boronization process was analyzed by using the intensity ratio of the H{sub α} to the D{sub α} line (I{sub H}/I{sub D}). The relation between the pressure and the intensity ratio was investigated, and the thickness of the deposited boron film was predicted. Also, the dilution ratio H/(H + D) of the boron film was analyzed and compared with the one predicted from an optical analysis of the emission spectrum.

  4. Boosting the Boron Dopant Level in Monolayer Doping by Carboranes.

    Science.gov (United States)

    Ye, Liang; González-Campo, Arántzazu; Núñez, Rosario; de Jong, Michel P; Kudernac, Tibor; van der Wiel, Wilfred G; Huskens, Jurriaan

    2015-12-16

    Monolayer doping (MLD) presents an alternative method to achieve silicon doping without causing crystal damage, and it has the capability of ultrashallow doping and the doping of nonplanar surfaces. MLD utilizes dopant-containing alkene molecules that form a monolayer on the silicon surface using the well-established hydrosilylation process. Here, we demonstrate that MLD can be extended to high doping levels by designing alkenes with a high content of dopant atoms. Concretely, carborane derivatives, which have 10 B atoms per molecule, were functionalized with an alkene group. MLD using a monolayer of such a derivative yielded up to ten times higher doping levels, as measured by X-ray photoelectron spectroscopy and dynamic secondary mass spectroscopy, compared to an alkene with a single B atom. Sheet resistance measurements showed comparably increased conductivities of the Si substrates. Thermal budget analyses indicate that the doping level can be further optimized by changing the annealing conditions. PMID:26595856

  5. Electronic Alteration on Oligothiophenes by o-Carborane: Electron Acceptor Character of o-Carborane in Oligothiophene Frameworks with Dicyano-Vinyl End-On Group.

    Science.gov (United States)

    Kim, So-Yoen; Lee, Ah-Rang; Jin, Guo Fan; Cho, Yang-Jin; Son, Ho-Jin; Han, Won-Sik; Kang, Sang Ook

    2015-05-01

    We studied electronic change in oligothiophenes by employing o-carborane into a molecular array in which one or both end(s) were substituted by electron-withdrawing dicyano-vinyl group(s). Depending on mono- or bis-substitution at the o-carborane, a series of linear A1-D-A2 (1a-1c) or V-shaped A1-D-A2-D-A1 (2a-2c) oligothiophene chain structures of variable length were prepared; A1, D, and A2, represent dicyano-vinyl, oligothiophenyl, and o-carboranyl groups, respectively. Among this series, 2a shows strong electron-acceptor capability of o-carborane comparable to that of the dicyano-vinyl substituent, which can be elaborated by a conformational effect driven by cage σ*-π* interaction. As a result, electronic communications between o-carborane and dicyano-vinyl groups are successfully achieved in 2a. PMID:25844983

  6. Palladium-catalyzed regioselective intramolecular coupling of o-carborane with aromatics via direct cage B-H activation.

    Science.gov (United States)

    Quan, Yangjian; Xie, Zuowei

    2015-03-18

    Palladium-catalyzed intramolecular coupling of o-carborane with aromatics via direct cage B-H bond activation has been achieved, leading to the synthesis of a series of o-carborane-functionalized aromatics in high yields with excellent regioselectivity. In addition, the site selectivity can also be tuned by the substituents on cage carbon atom. PMID:25747772

  7. Synthesis of o- and m-carborane derivatives of 5,10,15,20-tetra-(p-anionphenyl)porphyrin

    International Nuclear Information System (INIS)

    The data on synthesis of o- and m-carborane-containing porphyrins, which derivatives through boron atom of polyhedral nucleus are presented. The reaction of the porphyrin amino group acylation may be used for production of the porphyrin carborane derivative with high boron content (up to 30 %) with the purpose of applying them in boron neutron-capture cancer therapy

  8. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    Energy Technology Data Exchange (ETDEWEB)

    Kennedy, RD; Krungleviciute, V; Clingerman, DJ; Mondloch, JE; Peng, Y; Wilmer, CE; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK; Mirkin, CA

    2013-09-10

    A Cu-carborane-based metal organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits a pore volume of 1.02 cm(3)/g and a gravimetric BET surface area of ca. 2600 m(2)/g, and thus represents the first highly porous carborane-based MOF. As a consequence of the, unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m(2)/cm(3). CH4, CO2, and H-2 adsorption isotherms were measured over a broad range of pressures and temperatures and are in good agreement with computational predictions. The methane storage capacity of NU-135 at 35 bar and 298 K is ca. 187 v(STP)/v. At 298 K, the pressure required to achieve a methane storage density comparable to that of a compressed natural gas (CNG) tank pressurized to 212 bar, which is a typical storage pressure, is only 65 bar. The methane working capacity (5-65 bar) is 170 v(STP)/v. The volumetric hydrogen storage capacity at 55 bar and 77 K is 49 g/L. These properties are comparable to those of current record holders in the area of methane and hydrogen storage. This initial example lays the groundwork for carborane-based materials with high surface areas.

  9. Design and synthesis of carborane-containing estrogen receptor-beta (ERβ)-selective ligands.

    Science.gov (United States)

    Ohta, Kiminori; Ogawa, Takumi; Oda, Akifumi; Kaise, Asako; Endo, Yasuyuki

    2015-10-01

    Candidates for highly selective estrogen receptor-beta (ERβ) ligands (6a-c, 7a-c, 8a and 8b) were designed and synthesized based on carborane-containing ER ligands 1 and 2 as lead compounds. Among them, p-carboranylcyclohexanol derivatives 8a and 8b exhibited high ERβ selectivity in competitive binding assay: for example, 8a showed 56-fold selectivity for ERβ over ERα. Docking studies of 8a and 8b with the ERα and ERβ ligand-binding domains (LBDs) suggested that the p-carborane cage of the ligands is located close to key amino acid residues that influence ER-subtype selectivity, that is, Leu384 in the ERα LBD and Met336 in the ERβ LBD. The p-carborane cage in 8a and 8b appears to play a crucial role in the increased ERβ selectivity. PMID:26298498

  10. Carborane-containing tetraketodianhydrides, their dimers and polyimides on their base

    International Nuclear Information System (INIS)

    The new dianhydride of 1,7-bis[4-[4[(3,4-dicarboxybenzoyl)phenoxy]benzoy] carborane fusible at 421-423 K and its nonfusible dimer have been synthesized. New nonfusible carborane-containing dimers of tetraketodianhydrides were obtained as a result of acylation of diphenyl and fluorine. Polymides soluble in amide solvents and concentrated sulfuric acid and resistant towards the thermooxidative degradation were synthesized by low-temperature (353 K) and high-temperature (453 K) polycondensation in one stage with the 80-90 % yield. Polymide moldings were prepared from blends of powders of tetraketodianhydrides dimers and diaminodiphenyl ester by reactive formation method

  11. Palladium-Catalyzed Regioselective Diarylation of o-Carboranes By Direct Cage B-H Activation.

    Science.gov (United States)

    Quan, Yangjian; Xie, Zuowei

    2016-01-22

    Palladium-catalyzed intermolecular coupling of o-carborane with aromatics by direct cage B-H bond activation has been achieved, leading to the synthesis of a series of cage B(4,5)-diarylated-o-carboranes in high yields with excellent regioselectivity. Traceless directing group -COOH plays a crucial role for site- and di-selectivity of such intermolecular coupling reaction. A Pd(II)-Pd(IV)-Pd(II) catalytic cycle is proposed to be responsible for the stepwise arylation. PMID:26463595

  12. In vivo evaluation of carborane gadolinium-DTPA complex as an MR imaging boron carrier

    International Nuclear Information System (INIS)

    The evaluation of the Gd-carborane complex 2 as an MR imaging and boron carrier agent was carried out in vivo using tumor-bearing Donryu rats, MRI, ICP-AES, and α-autoradiography. The MR imaging revealed that the carborane Gd-DTPA 2 was metabolized slower in the body than Gd-DTPA 1. The results of the ICP-AES method indicated that compound 2 was incorporated into normal tissues and metabolized quickly, whereas it was not accumulated into tumor or brain tissue. The α-autoradiography showed that a high level of boron was obtained in the internal organs and in the necrosis of tumor tissue. (author)

  13. Carborane derivative development for boron neutron capture therapy. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Barnum, Beverly A.; Yan Hao; Moore, Roger; Hawthorne, M. Frederick; Baum, Kurt

    1999-04-01

    Boron Neutron Capture Therapy [BNCT] is a binary method of cancer therapy based on the capture of neutrons by a boron-10 atom [{sup 10}B]. Cytotoxic {sup 7}Li nuclei and {alpha}-particles are emitted, with a range in tissue of 9 and 5 {micro}m, respectively, about one cell diameter. The major obstacle to clinically viable BNCT is the selective localization of 5-30 ppm {sup 10}B in tumor cells required for effective therapy. A promising approach to BNCT is based on hydrophilic boron-rich oligomeric phosphate diesters, or ''trailers'' that have been shown to concentrate selectively in tumor tissue. Examples of these compounds were prepared previously at high cost using an automated DNA synthesizer. Direct synthesis methods are needed for the production of gram-scale quantities for further biological evaluation. The work accomplished as a result of the collaboration between Fluorochem, Inc. and UCLA demonstrates that short oligomers containing at least five carborane units with four phosphodiester linkages can be prepared in substantial quantities. This work was accomplished by the application of standard phosphoramidite coupling chemistry.

  14. Formation of stable anion-radical of C,C'-dipyridyl-carborane in the reaction of lithium and sodium alumohydrides, lithium isopropylate and lithium n-butylmercaptide with 1,2-diphenyl-o-carborane in tetrahydrofurane solution

    International Nuclear Information System (INIS)

    On the interaction of lithium and sodium alumohydrides, lithium isopropylate and n-butylmercaptide with 1,2-diphenyl-o-carborane in a tetrahydrofuran solution, a transfer of one electron to the carborane polyhedron occurs to form a stable anion-radical of C,C'-diphenylcarborane. This is a reversible reaction, and under the action of oxidizers the anion-radical of C,C'-diphenylcarborane transforms into the starting 1,2-diphenyl-0-carborane. On treatment with water the anion-radical decomposes affording the anion of 7,8-diphenyl-7,8-dicarboundecaborate

  15. Methods for cross-linking of unsaturated carborane-containing polyesters and study of properties of their copolymers

    International Nuclear Information System (INIS)

    The influence of the structure of unsaturated carborane-containing polyesters on their ability to be copolymerized with vinyl compounds in solution in the presence of radical and ionic catalysts, in emulsion in the presence of catalysts of radical type and in bulk with the acid of thermochemical initiation, under the action of γ-irradiation is discussed. Some properties of polymer products have been studied. The copolymers on the basis of carborane-containing unsaturated polyesters were found to have the higher thermooxidative resistance and higher adhesional parameters comparing with analogous copolymers without carborane fragments

  16. Isoflurane as a solvent for electrochemistry. Electrooxidation study of icosahedral carborane anions in four different solvents

    Czech Academy of Sciences Publication Activity Database

    Wahab, Abdul; Kvapilová, Hana; Klíma, Jiří; Michl, Josef; Ludvík, Jiří

    2013-01-01

    Roč. 689, JAN 2013 (2013), s. 257-261. ISSN 1572-6657 R&D Projects: GA MŠk ME09002; GA ČR GC203/09/J058 Institutional support: RVO:61388955 ; RVO:61388963 Keywords : isoflurane * relative permitivity * icosahedral carborane anions Subject RIV: CG - Electrochemistry Impact factor: 2.871, year: 2013

  17. Unique Stereocontrol in Carborane Chemistry: Skeletal Alkylcarbonation (SAC) versus Exoskeletal Alkylmethylation (EAM) Reactions

    Czech Academy of Sciences Publication Activity Database

    Bakardjiev, Mario; Holub, Josef; Macháček, Jan; Hnyk, Drahomír; Štíbr, Bohumil; Růžičková, Z.; Růžička, A.

    2015-01-01

    Roč. 54, č. 16 (2015), s. 4937-4940. ISSN 1433-7851 R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : NMR spectroscopy * carboranes * dicarbaboranes * stereocontrol * tricarbaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 11.261, year: 2014

  18. Novel semiconducting alloy polymers formed from ortho-carborane and 1,4-diaminobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Pasquale, Frank L. [Department of Chemistry and Center for Electronic Materials Processing and Integration, 1155 Union Circle 305070, University of North Texas, Denton, TX 76203-5017 (United States); Liu, Jing; Dowben, P.A. [Department of Physics and Astronomy, Nebraska Center for Nanostructures and Materials, 855 North 16th Street, Theodore Jorgensen Hall, University of Nebraska-Lincoln, Lincoln, NB 68588-0299 (United States); Kelber, Jeffry A., E-mail: kelber@unt.edu [Department of Chemistry and Center for Electronic Materials Processing and Integration, 1155 Union Circle 305070, University of North Texas, Denton, TX 76203-5017 (United States)

    2012-04-16

    Highlights: Black-Right-Pointing-Pointer Novel semiconducting films were formed from ortho-carborane and 1,4-diaminobenzene. Black-Right-Pointing-Pointer Electron bombardment induced site-specific crosslinking. Black-Right-Pointing-Pointer Crosslinking through boron in the ortho-carborane and carbon in 1,4-diaminobenzene. Black-Right-Pointing-Pointer An observed shift in the valence band maximum indicates a reduction of band gap. Black-Right-Pointing-Pointer A surface photovoltage effect is observed after cross-linking. - Abstract: Novel semiconducting polymers have been formed via the electron-induced cross-linking of ortho-carborane (B{sub 10}C{sub 2}H{sub 12}) and 1,4-diaminobenzene. The films were formed by co-condensation of the molecular precursors and 200 eV electron-induced cross-linking under ultra-high vacuum (UHV) conditions. Ultraviolet photoemission spectra show that the compound films display a shift of the valence band maximum from {approx}4.3 eV below the Fermi level for pure boron carbide to {approx}1.7 eV below the Fermi level when diaminobenzene is added. The surface photovoltage effect decreases with decreasing B/N atomic ratio. Core level photoelectron spectra indicate site-specific bonding between B sites non-adjacent to icosahedral carbon sites on the carborane moiety, and carbon sites on the diaminobenzene moiety. Molecular orbital calculations and experiment suggest significant electronic interaction between ortho-carborane and 1,4-diaminobenzene units, with the highest occupied valence band states predominantly 1,4-diaminobenzene in character.

  19. Novel semiconducting alloy polymers formed from ortho-carborane and 1,4-diaminobenzene

    International Nuclear Information System (INIS)

    Highlights: ► Novel semiconducting films were formed from ortho-carborane and 1,4-diaminobenzene. ► Electron bombardment induced site-specific crosslinking. ► Crosslinking through boron in the ortho-carborane and carbon in 1,4-diaminobenzene. ► An observed shift in the valence band maximum indicates a reduction of band gap. ► A surface photovoltage effect is observed after cross-linking. - Abstract: Novel semiconducting polymers have been formed via the electron-induced cross-linking of ortho-carborane (B10C2H12) and 1,4-diaminobenzene. The films were formed by co-condensation of the molecular precursors and 200 eV electron-induced cross-linking under ultra-high vacuum (UHV) conditions. Ultraviolet photoemission spectra show that the compound films display a shift of the valence band maximum from ∼4.3 eV below the Fermi level for pure boron carbide to ∼1.7 eV below the Fermi level when diaminobenzene is added. The surface photovoltage effect decreases with decreasing B/N atomic ratio. Core level photoelectron spectra indicate site-specific bonding between B sites non-adjacent to icosahedral carbon sites on the carborane moiety, and carbon sites on the diaminobenzene moiety. Molecular orbital calculations and experiment suggest significant electronic interaction between ortho-carborane and 1,4-diaminobenzene units, with the highest occupied valence band states predominantly 1,4-diaminobenzene in character.

  20. Mechanisms of carborane 1,6-C2B4H6 high-temperature oxidation in water vapor

    International Nuclear Information System (INIS)

    The reactivity of carborane-4 (1,6-C2B4H6) in water vapor at 930-1750 K and 0.02-3.0 MPa is experimentally studied. It is found that carborane-4 is a highly reactive compound: at P = 0.9 MPa and T > 1200 K its reactivity in water vapor exceeds that of propane in air by a factor of 3 to 7. The ignition delay for carborane-4/water vapor mixture decreases with the increasing pressure at T > 1200 K, but is pressure independent at T < 1000 K. It is shown that the ignition delays computed within the proposed detailed oxidation scheme for carborane-4 describe satisfactorily the experimental data in the entire range of the investigated temperatures and pressures

  1. Aggregation-Induced Delayed Fluorescence Based on Donor/Acceptor-Tethered Janus Carborane Triads: Unique Photophysical Properties of Nondoped OLEDs.

    Science.gov (United States)

    Furue, Ryuhei; Nishimoto, Takuro; Park, In Seob; Lee, Jiyoung; Yasuda, Takuma

    2016-06-13

    Luminescent materials consisting of boron clusters, such as carboranes, have attracted immense interest in recent years. In this study, luminescent organic-inorganic conjugated systems based on o-carboranes directly bonded to electron-donating and electron-accepting π-conjugated units were elaborated as novel optoelectronic materials. These o-carborane derivatives simultaneously possessed aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) capabilities, and showed strong yellow-to-red emissions with high photoluminescence quantum efficiencies of up to 97 % in their aggregated states or in solid neat films. Organic light-emitting diodes utilizing these o-carborane derivatives as a nondoped emission layer exhibited maximum external electroluminescence quantum efficiencies as high as 11 %, originating from TADF. PMID:27145481

  2. The First CNS-Active Carborane: A Novel P2X7 Receptor Antagonist with Antidepressant Activity

    Science.gov (United States)

    2014-01-01

    Relative to other polycyclic frameworks (1–3), a carborane cage (4 and Cs·5) exerts a significant biological effect as an inhibitor of the purinergic P2X7 receptor (P2X7R) which allows one to target depression in vivo and thus demonstrate, for the first time, that a carborane has the capacity to modify CNS activity. PMID:24689484

  3. Electro-optical properties of poly[di(2-thiophenyl)carborane] and its opto-electronic application

    Energy Technology Data Exchange (ETDEWEB)

    Cansu-Ergun, Emine Gul; Cihaner, Atilla, E-mail: cihaner@atilim.edu.tr

    2013-12-16

    Electrochemical and optical properties of a hybrid carborane based polymer called poly(di(2-thiophenyl)carborane) (P1) obtained electrochemically were reported as well as its electrochromic device application. Thiophene donor units and m-carborane acceptor unit were combined under the same umbrella via donor–acceptor–donor approach to obtain di(2-thiophenyl)carborane (1). Contrary to the literature, extreme conditions like highly dried solvent or inert atmosphere were not used for polymerization and characterization. Polymer P1 has an ambipolar character since it exhibited a reversible oxidation peak at a half wave potential (E{sub 1/2}) of 1.08 V and a quasi reversible reduction peak at E{sub 1/2} = −1.82 V vs. Ag/AgCl. The polymer film has an optical band gap of 1.95 eV with a maximum absorption band centered at 488 nm. Also, it exhibited multicolor electrochromic behavior between its reduced and oxidized states changing from dark orange to light blue. Furthermore, the electrochromic device prepared based on P1 film was stable and robust. - Highlights: • Electrochromic properties of a carborane based conjugated polymer were reported. • The polymer exhibited an ambipolar character and multicolor behaviors. • It is the first electrochromic device based on a carborane unit.

  4. Electro-optical properties of poly[di(2-thiophenyl)carborane] and its opto-electronic application

    International Nuclear Information System (INIS)

    Electrochemical and optical properties of a hybrid carborane based polymer called poly(di(2-thiophenyl)carborane) (P1) obtained electrochemically were reported as well as its electrochromic device application. Thiophene donor units and m-carborane acceptor unit were combined under the same umbrella via donor–acceptor–donor approach to obtain di(2-thiophenyl)carborane (1). Contrary to the literature, extreme conditions like highly dried solvent or inert atmosphere were not used for polymerization and characterization. Polymer P1 has an ambipolar character since it exhibited a reversible oxidation peak at a half wave potential (E1/2) of 1.08 V and a quasi reversible reduction peak at E1/2 = −1.82 V vs. Ag/AgCl. The polymer film has an optical band gap of 1.95 eV with a maximum absorption band centered at 488 nm. Also, it exhibited multicolor electrochromic behavior between its reduced and oxidized states changing from dark orange to light blue. Furthermore, the electrochromic device prepared based on P1 film was stable and robust. - Highlights: • Electrochromic properties of a carborane based conjugated polymer were reported. • The polymer exhibited an ambipolar character and multicolor behaviors. • It is the first electrochromic device based on a carborane unit

  5. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.

    Science.gov (United States)

    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M

    2016-07-27

    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  6. Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties

    Science.gov (United States)

    Atmaca, Göknur Yaşa; Dizman, Cemil; Eren, Tarık; Erdoğmuş, Ali

    2015-02-01

    The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, 1H and 11B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ = 0.41, 0.39).

  7. Photo-fragmentation of the closo-carboranes Part 1: Energetics of Decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Kilcoyne, Arthur L; Feng, Danqin; Liu, Jing; Hitchcock, Adam P.; Kilcoyne, A.L. David; Tyliszczak, Tolek; Riehs, Norman F.; R& #252; hl, Eckart; Bozek, John D.; McIlroy, David; Dowben, Peter A.

    2007-11-09

    The ionic fragmentation following B 1s and C 1s excitation of three isomeric carborane cage compounds [closo-dicarbadodecaboranes: orthocarborane (1,2-C2B10H12), metacarborane (1,7-C2B10H12), and paracarborane (1,12-C2B10H12)], is compared with the energetics of decomposition. The fragmentation yields for all three molecules are quite similar. Thermodynamic cycles are constructed for neutral and ionic species in an attempt to systemically characterize single ion closo-carborane creation and fragmentation processes. Lower energy decomposition processes are favored. Among the ionic species, the photon induced decomposition isdominated by BH+ and BH2+ fragment loss. Changes in ion yield associated with core to bound excitations are observed.

  8. Synthesis of a hybrid m-terphenyl/o-carborane building block: applications in phosphine ligand design.

    Science.gov (United States)

    Lugo, Christopher A; Moore, Curtis E; Rheingold, Arnold L; Lavallo, Vincent

    2015-03-01

    A hybrid terphenyl/o-carborane ligand building block is synthesized by the reaction of m-terphenylalkyne with B10H14. This sterically demanding substituent can be installed into ligands, as demonstrated by the preparation of carboranylphosphine. The bulky phosphine reacts with [ClRh(CO)2]2 to produce monophosphine complex ClRhL(CO)2, which subsequently extrudes CO under vacuum to afford the dimeric species [ClRhL(CO)]2. The latter complex does not react with excess phosphine and is resistant toward cyclometalation, which is in contrast to related o-carborane phosphine complexes. Data from a single-crystal X-ray diffraction study are utilized to quantify the steric impact of the ligand via the percent buried volume approach. PMID:25668570

  9. Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties.

    Science.gov (United States)

    Atmaca, Göknur Yaşa; Dizman, Cemil; Eren, Tarık; Erdoğmuş, Ali

    2015-02-25

    The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, (1)H and (11)B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ=0.41, 0.39). PMID:25222320

  10. Raman spectral investigation of structural peculiarities of cobalt carborane complexes containing dicarbollide and dicarbacanastide ligands

    International Nuclear Information System (INIS)

    Certain cobalt carborane complexes incorporating Cs[(1.2--C2B9H11)2Co], Cs[(8, 9, 12-Br3-C2B9H8)2Co], Cs[8-I-C2B9H10)2Co and multinuclear chain cobalt carborane complexes of general formula Csn[(1.2-C2B9H11)2Con (1.2-C2B8H10)n-1], where n=2, 3, 4, 5, 6, 7 have been studied by the method of Raman spectroscopy. Characteristic features of the frequency and intensity of lines of ligand-metal-ligand full-symmetry stretching vibration in Raman spectra of the complexes permit their use as analytic characteristic. Refs. 8, figs. 3

  11. Carborane-beta-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

    Czech Academy of Sciences Publication Activity Database

    Neirynck, P.; Schimer, Jiří; Jonkheijm, P.; Milroy, L. G.; Cígler, Petr; Brunsveld, L.

    2015-01-01

    Roč. 3, č. 4 (2015), s. 539-545. ISSN 2050-750X R&D Projects: GA MŠk(CZ) LH11027 Institutional support: RVO:61388963 Keywords : beta-cyclodextrine/carborane host-guest system * supramolecular chemistry * bioactive surfaces Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.726, year: 2014 http://pubs.rsc.org/en/content/articlepdf/2015/tb/c4tb01489h

  12. Synthesis of o- and m-carborane substituted porphyrins of natural type

    International Nuclear Information System (INIS)

    Synthesis of new mono- and dicarborane-containing porphyrins on the basis of protoporphyrin IX, its monobenzene esters, deuteroporphyrin IX, 9-hydroxymethyl-m- and 9-hydroxymethyl-o-carboranes was conducted. The yield of the products amounted to 24 - 76 %. All the compounds prepared were characterized using electronic, 1H NMR and IR spectroscopy and mass spectrometry. Relying on spectral data, the structure of porphyrin nucleus in the compounds was confirmed

  13. Oxidation of icosahedral carboranes in liquid SO2: An experimental ans theoretical study

    Czech Academy of Sciences Publication Activity Database

    Wahab, Abdul; Stepp, Brian R.; Valášek, Michal; Douvris, C.; Štursa, Jan; Michl, Josef; Klíma, Jiří; Ludvík, Jiří

    Dresden: IFW, 2011. s. 23-23. [Prague-Dresden Electrochemical Seminar 2011. 24.11.2011-26.11.2011, Oybin] R&D Projects: GA MŠk LC510; GA MŠk ME09002; GA AV ČR IAA400550708; GA ČR GC203/09/J058 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : icosahedral carboranes * electrochemistry Subject RIV: CG - Electrochemistry

  14. Preparation and Separation of Telechelic Carborane-Containing Poly(ethylene glycol)s

    Czech Academy of Sciences Publication Activity Database

    Matějíček, P.; Uchman, M.; Lepšík, Martin; Srnec, Martin; Zedník, J.; Kozlík, P.; Kalíková, K.

    2013-01-01

    Roč. 78, č. 6 (2013), s. 528-535. ISSN 2192-6506 R&D Projects: GA AV ČR IAAX00320901 Grant ostatní: GA ČR(CZ) GPP208/12/P236 Institutional support: RVO:61388963 Keywords : carboranes * click chemistry * poly(ethylene glycol) * quantum chemistry * reaction mechanisms Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.242, year: 2013

  15. Nanoscaled carborane ruthenium(II)-arene complex inducing lung cancer cells apoptosis

    OpenAIRE

    Yan Hong; Ye Hongde; Wu Chunhui; Zhang Gen; Wang Xuemei

    2011-01-01

    Abstract Background The new ruthenium(II)-arene complex, which bearing a carborane unit, ruthenium and ferrocenyl functional groups, has a novel versatile synthetic chemistry and unique properties of the respective material at the nanoscale level. The ruthenium(II)-arene complex shows significant cytotoxicity to cancer cells and tumor-inhibiting properties. However, ruthenium(II)-arene complex of mechanism of anticancer activity are scarcely explored. Therefore, it is necessary to explore rut...

  16. Stabilization of a highly porous metal-organic framework utilizing a carborane-based linker.

    Science.gov (United States)

    Clingerman, Daniel J; Morris, William; Mondloch, Joseph E; Kennedy, Robert D; Sarjeant, Amy A; Stern, Charlotte; Hupp, Joseph T; Farha, Omar K; Mirkin, Chad A

    2015-04-18

    The first tritopic carborane-based linker, H3BCA (C15B24O6H30), based on closo-1,10-C2B8H10, has been synthesized and incorporated into a metal-organic framework (MOF), NU-700 (Cu3(BCA)2). In contrast to the analogous MOF-143, NU-700 can be activated with retention of porosity, yielding a BET surface area of 1870 m(2) g(-1). PMID:25767827

  17. Tuning the optical properties of 2-thienylpyridyl iridium complexes through carboranes and anions.

    Science.gov (United States)

    Zhu, Lin; Tang, Xiao; Yu, Qi; Lv, Wen; Yan, Hong; Zhao, Qiang; Huang, Wei

    2015-03-16

    2-Thienylpyridyl iridium(III) complexes containing an o-, m-, or p-carboranylvinyl-2,2'-bipyridine ligand and various counteranions (denoted o-PF6, m-BF4, m-PF6, m-SbF6, m-ClO4, m-OTf, m-NO3, m-BPh4, m-F, m-Cl, and p-PF6) were synthesized by using C-formyl carboranes as starting materials. The solid-state structures of o-PF6, m-PF6, m-ClO4, and m-BF4 showed that the cations form twisted cavities in which the anions are fixed by multiple hydrogen bonds. Anion-hydrogen interactions were investigated for nine m-carborane-based complexes with different counteranions. All carborane-based iridium(III) complexes show similar phosphorescence yields in solution but significantly different emission in the solid state. Anion-exchange titration and theoretical calculations revealed the relationships between structures and optical properties. The size of the anion and C-H⋅⋅⋅X anion-hydrogen bonds strongly influence the phosphorescence quantum yield in the solid state. In particular, the Ccar-H⋅⋅⋅X hydrogen bonds between the carboranyl unit and the anion play an important role in solid-state phosphorescence. Complex p-PF6 was successfully applied in phosphorescence-lifetime bioimaging owing to its low toxicity and near-infrared emission. PMID:25663604

  18. Carborane tuning on iridium complexes: redox-switchable second-order NLO responses.

    Science.gov (United States)

    Wang, Jiao; Wang, Wen-Yong; Fang, Xin-Yan; Qiu, Yong-Qing

    2015-04-01

    Much effort has been devoted to investigating the molecular geometries, electronic structures, redox properties and nonlinear optical (NLO) properties of Ir complexes involving o-, m- or p-carborane groups by density functional theory (DFT) methods. Switchable second-order NLO properties were induced by redox processes involving these complexes, and it was found that mainly the coordination bonds of Ir complexes changed during the oxidation process. Our calculations revealed that oxidation reactions have a significant influence on the second-order NLO response owing to the change in charge transfer pattern. The β tot values of oxidized species are at least ∼9 times larger for set I and ∼5 times larger for set II than those of the corresponding parent complexes. Introduction of carborane groups into ppy (phenylpyridine) ligands can enhance the second-order NLO response by 1.2- 1.6 times by a metal-to-ligand charge transfer (MLCT) transition between the Ir atom and carborane. The β tot of complex 2 [(ppy)2Ir(phen)](+) (phen = phenanthroline) is 3.3 times larger than that of complex 1 (ppy)2Ir(acce) (acce = acetylacetonate), which is caused by ligand-to-ligand charge transfer (LLCT) between ppy ligands and the ancillary ligand. Therefore, it can be concluded that the second-order NLO response can be effectively enhanced by oxidation reactions. PMID:25791353

  19. Complexes of carborane acids linked by strong hydrogen bonds: acidity scales.

    Science.gov (United States)

    Grabowski, Sławomir J

    2016-06-28

    Carborane acids, currently known as the strongest acis, are analyzed and compared with other species classified as superacids as well as with selected mineral acids and carbocations. Calculations (B3LYP/6-311++G(d,p) level) on these moieties as well as on their conjugate bases were performed to evaluate corresponding proton affinities. In addition, the complexes of these species with the CHB11F11(-) anion and the complexes of the conjugate bases with the trimethylammonium cation were analyzed. The scales, based on spectroscopic results, DFT energies and on the topological QTAIM (Quantum Theory of Atoms in Molecules) parameters, are introduced and discussed to order the acidity of the species analyzed here. The properties of the bond critical points corresponding to the intermolecular contacts are discussed. The majority of the results show that HCHB11F11 carborane acid is the strongest in agreement with the previous experimental studies of Reed and coworkers. Very often the abovementioned acidity scales show that carborane acids are able to protonate hydrocarbons. PMID:27253195

  20. Doxorubicin-Loaded Carborane-Conjugated Polymeric Nanoparticles as Delivery System for Combination Cancer Therapy.

    Science.gov (United States)

    Xiong, Hejian; Zhou, Dongfang; Qi, Yanxin; Zhang, Zhiyun; Xie, Zhigang; Chen, Xuesi; Jing, Xiabin; Meng, Fanbo; Huang, Yubin

    2015-12-14

    Carborane-conjugated amphiphilic copolymer nanoparticles were designed to deliver anticancer drugs for the combination of chemotherapy and boron neutron capture therapy (BNCT). Poly(ethylene glycol)-b-poly(L-lactide-co-2-methyl-2(2-dicarba-closo-dodecarborane)propyloxycarbonyl-propyne carbonate) (PLMB) was synthesized via the versatile reaction between decaborane and side alkynyl groups, and self-assembled with doxorubicin (DOX) to form drug-loaded nanoparticles. These DOX@PLMB nanoparticles could not only suppress the leakage of the boron compounds into the bloodstream due to the covalent bonds between carborane and polymer main chains, but also protect DOX from initial burst release at physiological conditions because of the dihydrogen bonds between DOX and carborane. It was demonstrated that DOX@PLMB nanoparticles could selectively deliver boron atoms and DOX to the tumor site simultaneously in vivo. Under the combination of chemotherapy and BNCT, the highest tumor suppression efficiency without reduction of body weight was achieved. This polymeric nanoparticles delivery system could be very useful in future chemoradiotherapy to obtain improved therapeutic effect with reduced systemic toxicity. PMID:26564472

  1. Deposition of a-C/B films from o-carborane and trimethyl boron precursors

    International Nuclear Information System (INIS)

    Vacuum wall deposition of a-B/C films has had tremendous positive impact on the performance of tokamak fusion reactors. In this work, precursor vapor and helium carrier gas have been used to create a plasma using a novel plasma source. Either trimethyl boron (TMB) or sublimed vapor from o-carborane solid can be used as deposition precursors. The plasma operates in a pressure range of 5 to 15 mTorr and typical flow rates are 5 sccm He plus 0.5-1 sccm o-carborane or TMB vapor. The film deposition rate ranges from less than 100 angstrom/minute to over 1,000 angstrom/minute. Microwave power levels range from 300--400 W at 2.45 GHz. The temperature and bias of the substrate can be varied, and the temperature of the substrate is recorded during deposition. The films have been analyzed using XPS. The atomic composition of the films has been measured. The o-carborane films have a much higher boron concentration than those deposited from TMB. Thecharacteristics of the different species have also been examined for each type of film. The thickness of the films is measured by profilometry, and this is combined with measurements of the film area and weight to calculate the film density. X-ray diffraction analysis has been performed; no evidence of any crystalline structure was found. Films with a thickness of a few thousand angstrom are routinely obtained. Deposition rates were 350 angstrom/minute on average

  2. Investigating the Weak to Evaluate the Strong: An Experimental Determination of the Electron Binding Energy of Carborane Anions and the Gas phase Acidity of Carborane Acids

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Matthew M; Wang, Xue B; Reed, Christopher A; Wang, Lai S; Kass, Steven R

    2009-12-23

    Five CHB11X6Y5- carborane anions from the series X = Br, Cl, I and Y = H, Cl, CH3 were generated by electrospray ionization, and their reactivity with a series of Brønsted acids and electron transfer reagents were examined in the gas phase. The undecachlorocarborane acid, H(CHB11Cl11), was found to be far more acidic than the former record holder, (1-C4F9SO2)2NH (i.e., ΔH°acid = 241 ± 29 vs 291.1 ± 2.2 kcal mol-1) and bridges the gas-phase acidity and basicity scales for the first time. Its conjugate base, CHB11Cl11-, was found by photoelectron spectroscopy to have a remarkably large electron binding energy (6.35 ± 0.02 eV) but the value for the (1-C4F9SO2)2N- anion is even larger (6.5 ± 0.1 eV). Consequently, it is the weak H-(CHB11Cl11) BDE (70.0 kcal mol-1, G3(MP2)) compared to the strong BDE of (1-C4F9SO2)2N-H (127.4 ± 3.2 kcal mol-1) that accounts for the greater acidity of carborane acids.

  3. Carborane-containing urea-based inhibitors of glutamate carboxypeptidase II: Synthesis and structural characterization

    Czech Academy of Sciences Publication Activity Database

    Youn, S.; Kim, K.I.; Ptáček, Jakub; Ok, K.; Nováková, Zora; Kim, Y.; Koo, J.; Bařinka, Cyril; Byun, Y.

    2015-01-01

    Roč. 25, č. 22 (2015), s. 5232-5236. ISSN 0960-894X R&D Projects: GA ČR GAP301/12/1513; GA MŠk(CZ) ED1.1.00/02.0109 Grant ostatní: GA MŠk(CZ) CZ.1.07/2.3.00/30.0045 Institutional support: RVO:86652036 Keywords : Carborane * Glutamate carboxypeptidase II * X-ray crystal structure Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 2.420, year: 2014

  4. Self-Assembled p-Carborane Analog of p-Mercaptobenzoic Acid on Au{111}

    Czech Academy of Sciences Publication Activity Database

    Thomas, J. C.; Boldog, Ishtvan; Auluck, H. S.; Bereciartua, P.J.; Dušek, Michal; Macháček, Jan; Bastl, Zdeněk; Weiss, P. S.; Baše, Tomáš

    2015-01-01

    Roč. 27, č. 15 (2015), s. 5425-5435. ISSN 0897-4756 R&D Projects: GA ČR GAP205/10/0348; GA ČR(CZ) GA14-03276S; GA MŠk LL1301 Institutional support: RVO:61388980 ; RVO:68378271 ; RVO:61388955 Keywords : self-assembly * boron compounds * carborane * scanning tunneling microscopy * crystallography Subject RIV: CA - Inorganic Chemistry; BM - Solid Matter Physics ; Magnetism (FZU-D); CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 8.354, year: 2014

  5. Extremely Electron-Rich, Boron-Functionalized, Icosahedral Carborane-Based Phosphinoboranes

    Science.gov (United States)

    Spokoyny, Alexander M.; Lewis, Calvin D.; Teverovskiy, Georgiy; Buchwald, Stephen L.

    2012-01-01

    We have prepared the first examples of B9-connected trivalent aryl and alkyl phosphinoborane species via Pd-catalyzed phosphination of 9-iodo-meta-carborane. Our studies highlight the unique electronic features of the B9-connected meta-carboranyl moiety as compared to its C1-based analogue. This work suggests that the B9-functionalized meta-carboranyl substituent in these ligands exhibits more electron-releasing character than any other known carbon-based substituent, ultimately laying the foundation for a new class of phosphine ligands with extremely electron-rich character. PMID:23667288

  6. Separation of gas mixtures using Co(II) carborane-based porous coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Y. S.; Spokoyny, Alexander M.; Farha, Omar K.; Snurr, R. Q.; Hupp, Joseph T.; Mirkin, Chad

    2010-01-01

    Separations of CO{sub 2}/CH{sub 4}, CO{sub 2}/N{sub 2}, and O{sub 2}/N{sub 2} mixtures were studied in three porous coordination polymers made of the same carborane ligand and Co(II) nodes. High selectivities for CO{sub 2} over CH{sub 4} (~47) and CO{sub 2} over N{sub 2} (~95) were obtained, especially in the material with coordinated pyridine. Unusual selectivity for O{sub 2} over N{sub 2} (as high as 6.5) was demonstrated in the materials with open Co(II) sites.

  7. Cyanoethylation and (methoxycarbonyl)ethylation of icosahedral ortho-carborane derivatives at carbon vertices via Michael additions

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Bačkovský, Jaroslav; Fusek, Jiří; Plzák, Zbyněk

    2001-01-01

    Roč. 66, č. 10 (2001), s. 1499-1507. ISSN 0010-0765 R&D Projects: GA ČR GA104/99/1096; GA MŠk LB98233 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * Michael additions Subject RIV: CA - Inorganic Chemistry Impact factor: 0.778, year: 2001

  8. Tethered N-heterocyclic carbene-carboranes: unique ligands that exhibit unprecedented and versatile coordination modes at rhodium.

    Science.gov (United States)

    Holmes, Jordan; Pask, Christopher M; Fox, Mark A; Willans, Charlotte E

    2016-05-11

    Four brand new hybrid ligands combining an N-heterocyclic carbene tethered with two isomeric nido-dicarbaundecaborane dianions, a neutral closo-dicarbadodecaborane or a closo-dicarbadodecaborane anion are described. Versatile coordination of the ligands to Rh(I) is demonstrated, in which both NHC and carborane moieties covalently coordinate a metal centre. PMID:27098432

  9. Novel alloy polymers formed from ortho-carborane and benzene or pyridine

    International Nuclear Information System (INIS)

    Polymer films have been formed by electron-induced cross-linking of condensed ortho-carborane and benzene (B10C2HX:BNZ) or pyridine (B10C2HX:py) at 110 K, followed by warming up to room temperature. High resolution core-level photoemission and molecular orbital calculations demonstrate that the reaction of the icosahedra with the aromatic group is site-specific: bonding occurs between a C atom on the aromatic group and a B site bound to other boron atoms on the icosahedron. This site specificity determines a systematic variation in the valence band maximum relative to the Fermi level from −4.3 eV for cross-linked ortho-carborane to −2.6 eV for B10C2HX:BNZ and −2.2 eV for B10C2HX:py. The results indicate the ability to form a new class of materials that are a cross between a molecular solid and a network polymer. Further, the electronic properties of these materials can be systematically tuned for a broad variety of applications in neutron detection, nano-electronics and spintronics. (paper)

  10. Plasma deposition of boron films with high growth rate and efficiency using carborane

    International Nuclear Information System (INIS)

    The injection of carborane (C2B10H12) on the PISCES-B linear plasma device has been used to produce boron containing films on various target species. Film growth rates achieved are extremely high (up to 30 nm/s) compared to those typically found for glow discharges (∼0.01 nm/s). For low-Z target materials (C and Al) the film production is highly efficient, with the boron film growth rate comparable to the incident ion flux and the injection rate of boron atoms. The boron to carbon ratio is 3.0-3.6 for these films. Similarly high growth rates (∼10 nm/s) are obtained with high-Z target (W), but with lower deposition efficiency and higher B/C film ratio. The high film growth rate/efficiency are apparently linked to the high degree of carborane ionization and dissociation caused by the ∼40 eV PISCES-B plasma, compared with T<1 eV plasmas of glow discharges. This technique opens the possibility of continuously producing protective B films in thermonuclear devices where net erosion rates approach 10 nm/s

  11. First investigations of a silicon neutron detector with a carborane converter

    International Nuclear Information System (INIS)

    We present a new design of a slow neutron detector, based on silicon detectors with innovative materials acting as conversion layers, plus preliminary results that will be the basis for a more complete study in the near future. The sensitive element of this detector is a Schottky barrier silicon diode covered with o-carborane, a novel boron-based converter material that detects neutrons by means of the 10B(n,α)7Li reaction. This sensor has been simulated with the MCNPX Monte-Carlo software in order to find the optimal converter layer thickness that maximizes the neutron detection efficiency. The simulated maximum efficiency is 2.7% for a 20 μm converter layer of the o-carborane fabricated with pure 10B and of 0.5% for the same compound but made with natural boron material. Moreover, the performance of test devices has been investigated by means of an 241AmBe neutron source and the results have been analyzed with the help of GEANT4 simulations.

  12. Carborane Substituents Promote Direct Electrophilic Insertion over Reduction-Metalation Reactions.

    Science.gov (United States)

    Man, Wing Y; Ellis, David; Rosair, Georgina M; Welch, Alan J

    2016-03-24

    Two-electron reduction of 1,1'-bis(o-carborane) followed by reaction with [Ru(η-mes)Cl2 ]2 affords [8-(1'-1',2'-closo-C2 B10 H11 )-4-(η-mes)-4,1,8-closo-RuC2 B10 H11 ]. Subsequent two-electron reduction of this species and treatment with [Ru(η-arene)Cl2 ]2 results in the 14-vertex/12-vertex species [1-(η-mes)-9-(1'-1',2'-closo-C2 B10 H11 )-13-(η-arene)-1,13,2,9-closo-Ru2 C2 B10 H11 ] by direct electrophilic insertion, promoted by the carborane substituent in the 13-vertex/12-vertex precursor. When arene=mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in a process that makes the metal-ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of a series of previously reported 14-vertex dicobaltacarboranes. PMID:26934539

  13. The substituent effect of 2-R-o-carborane on the photophysical properties of iridium(iii) cyclometalates.

    Science.gov (United States)

    Park, Jihyun; Lee, Young Hoon; Ryu, Ji Yeon; Lee, Junseong; Lee, Min Hyung

    2016-04-01

    A family of heteroleptic iridium(iii) cyclometalates, [4-(2-RCB)ppy]2Ir(acac) (3c-3g; CB = o-carboran-1-yl; ppy = 2-phenylpyridinato-C(2),N; acac = acetylacetonate; R = (i)Pr (3c), (i)Bu (3d), Ph (3e), CF3C6H4 (3f), C6F5 (3g)) with various 2-R substituted o-carboranes at the 4-position in the phenyl ring of the ppy ligand, were prepared. The X-ray crystal structure of all complexes, including 3a (R = H) and 3b (R = Me), showed that while the carboranyl C-C bond distance increases with the increasing steric effect of the 2-R substituent (3a-3d), the bond distance is more likely to be influenced by the electronic effect of the substituent for the 2-aryl substituted complexes (3e-3g). The absorption and emission bands of all complexes were red-shifted with respect to those of the parent (ppy)2Ir(acac) (4). While 3a-3d exhibited intense green phosphorescence with good quantum efficiency in toluene (ΦPL = 0.17-0.47), the complexes were poorly emissive in THF (ΦPL carborane-centered, electrochemical reduction (Eonset = -2.01 to -1.22 V). The potential values of these reductions increased with increases in the electron accepting ability of the 2-R group (H carborane substituted complexes. This reduction behavior of 3a-3g implies that the LUMO contribution of 2-R-o-carborane units increases through the substitution at the 4-position of the ppy ligand and is influenced by the nature of the 2-R group, which may be responsible for facile carboranyl C-C bond variation leading to efficient quenching of the emissive excited states. PMID:26923990

  14. Novel synthetic approach to charge-compensated phosphonio-nido-carboranes. Synthesis and structural characterization of neutral mono and bis(phosphonio) nido-ortho-carboranes.

    Science.gov (United States)

    Kabytaev, Kuanysh Z; Safronov, Alexander V; Sevryugina, Yulia V; Barnes, Charles L; Jalisatgi, Satish S; Hawthorne, M Frederick

    2015-04-20

    A number of monosubstituted n-(triphenylphosphonio)-7,8-dicarba-nido-undecaboranes (2a, n = 1; 2b, n = 3; 2c, n = 5; 2d, n = 9) were prepared via a cross-coupling reaction between the tetrabutylammonium iodo-7,8-dicarba-nido-undecaborates (1a-d) and PPh3 in the presence of a Pd(PPh3)4 catalyst. The substitution rate was found to depend on the iodine position in the carborane cage. Under similar conditions, the reaction of 5,6-diiodo- (3) and 9,11-diiodo-7,8-dicarba-nido-undecaborate (5) anions exclusively yielded the monosubstitution products 5-iodo-6-(triphenylphosphonio)-7,8-dicarba-nido-undecaborane (4) and 9-iodo-11-(triphenylphosphonio)-7,8-dicarba-nido-undecaborane (6), respectively. The reaction of tetrabutylammonium 6,9-diiodo-7,8-dicarba-nido-undecaborate (7) exclusively produced the phosphine substitution product in the open face of the nido-carborane, 6-iodo-9-triphenylphosphonio-7,8-dicarba-nido-undecaborane (8). The addition of a base (Cs2CO3, NaH) to the reactions of 3 and 5 with PPh3 afforded the corresponding bis(triphenylphosphonio)-7,8-dicarba-nido-undecaboranes, 9 and 10. Compound 10 was also prepared from 6 using the general procedure. The reaction of the triiodocarborane tetrabutylammonium 5,6,9-triiodo-7,8-dicarba-nido-undecaborate (11) with excess PPh3 in the presence of Cs2CO3 and Pd(PPh3)4 only produced neutral 5-iodo-6,9-bis(triphenylphosphonio)-7,8-dicarba-nido-undecaborane (12); no positively charged tris(phosphonio) species formed. The compositions of all prepared compounds were determined by multinuclear NMR spectroscopy and high-resolution mass spectrometry. The structures of compounds 2c, 6, 8, 9, and 12 were established by the X-ray diffraction analysis of single crystals. PMID:25815784

  15. On the scintillation efficiency of carborane-loaded liquid scintillators for thermal neutron detection

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Zheng, E-mail: zchang@scsu.edu [The Applied Radiation Sciences Laboratory, South Carolina State University, Orangeburg, SC 29117 (United States); Okoye, Nkemakonam C. [The Applied Radiation Sciences Laboratory, South Carolina State University, Orangeburg, SC 29117 (United States); Urffer, Matthew J.; Green, Alexander D. [Department of Nuclear Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Childs, Kyle E. [The Applied Radiation Sciences Laboratory, South Carolina State University, Orangeburg, SC 29117 (United States); Miller, Laurence F. [Department of Nuclear Engineering, University of Tennessee, Knoxville, TN 37996 (United States)

    2015-01-01

    The scintillation efficiency in response to thermal neutrons was studied by loading different concentrations of carborane (0–8.5 wt%) and naphthalene (0 and 100 g/L) in five liquid organic scintillators. The sample was characterized in Pb and Cd shields under the irradiation of the thermal neutrons from a {sup 252}Cf source. A method was developed to extract the net neutron response from the pulse-height spectra. It was found that the order of scintillation efficiencies for both γ-rays and thermal neutrons is as follows: diisopropylnaphthalene>toluene (concentrated solutes)>toluene∼pseudocumene∼m-xylene. The quench constants, obtained by fitting the Stern–Volmer model to the plots of light output versus carborane concentration, are in the range of 0.35–1.4 M{sup −1} for all the scintillators. The Birks factors, estimated using the specific energy loss profiles of the incident particles, are in the range of 9.3–14 mg cm{sup −2} MeV{sup −1} for all the samples. The light outputs are in the range of 63–86 keV electron equivalents (keVee) in response to thermal neutrons. Loading naphthalene generally promotes the scintillation efficiency of the scintillator with a benzene derivative solvent. Among all the scintillators tested, the diisopropylnaphthalene-based scintillator shows the highest scintillation efficiency, lowest Birks factor, and smallest quench constants. These properties are primarily attributed to the double fused benzene-ring structure of the solvent, which is more efficient to populate to the excited singlet state under ionizing radiation and to transfer the excitation energy to the fluorescent solutes.

  16. On the scintillation efficiency of carborane-loaded liquid scintillators for thermal neutron detection

    International Nuclear Information System (INIS)

    The scintillation efficiency in response to thermal neutrons was studied by loading different concentrations of carborane (0–8.5 wt%) and naphthalene (0 and 100 g/L) in five liquid organic scintillators. The sample was characterized in Pb and Cd shields under the irradiation of the thermal neutrons from a 252Cf source. A method was developed to extract the net neutron response from the pulse-height spectra. It was found that the order of scintillation efficiencies for both γ-rays and thermal neutrons is as follows: diisopropylnaphthalene>toluene (concentrated solutes)>toluene∼pseudocumene∼m-xylene. The quench constants, obtained by fitting the Stern–Volmer model to the plots of light output versus carborane concentration, are in the range of 0.35–1.4 M−1 for all the scintillators. The Birks factors, estimated using the specific energy loss profiles of the incident particles, are in the range of 9.3–14 mg cm−2 MeV−1 for all the samples. The light outputs are in the range of 63–86 keV electron equivalents (keVee) in response to thermal neutrons. Loading naphthalene generally promotes the scintillation efficiency of the scintillator with a benzene derivative solvent. Among all the scintillators tested, the diisopropylnaphthalene-based scintillator shows the highest scintillation efficiency, lowest Birks factor, and smallest quench constants. These properties are primarily attributed to the double fused benzene-ring structure of the solvent, which is more efficient to populate to the excited singlet state under ionizing radiation and to transfer the excitation energy to the fluorescent solutes

  17. Ring-alkyl connecting group effect on mesogenic properties of p-carborane derivatives and their hydrocarbon analogues

    Directory of Open Access Journals (Sweden)

    Aleksandra Jankowiak

    2009-12-01

    Full Text Available The effect of the phenyl–alkyl connecting group on mesogenic properties of several series of isostructural compounds containing p-carborane (A and B, bicyclo[2.2.2]octane (C, and benzene (D was investigated using thermal and optical methods. Results demonstrated that mesophase stability in the series containing A–D follows the order (AlkCH2CH2– < (AlkOOC– < (AlkCH2O– < (AlkCOO–. Surprisingly, the connecting groups (AlkCH2CH2– and (AlkOOC– destabilize the mesophase significantly stronger for carboranes (A and B than for carbocyclic derivatives (C and D. Analysis indicates that this effect may have quadrupolar and conformational origin.

  18. Arene ruthenium complexes with monoanionic carborane ligand [9-SMe2-7,8-C2B9H10]-

    International Nuclear Information System (INIS)

    Cation ruthenium complexes [(η-arene)Ru(η-9-SMe2-7,8-C2B9H10)]+ (arene = C6H6 (1), 1, 3, 5 - C6H3Me3 (2), Me = methyl), containing carborane ligand, were prepared with the yield of ∼ 50% by interaction between salt Na[9-SMe2-7,8-C2B9H10] and complexes [(η - arene)RuCl2]2. Products of the reactions were characterized by the methods of elementary analysis and 1H, 11B NMR. According to X-ray diffraction analysis data complex cation 1 has a sandwich structure. Distances from ruthenium atom to plane C2B3 in carborane ligand and to plane C6 of arene make up 1.630 and 1.732 A, respectively

  19. Plasma-enhanced chemical vapor deposition of ortho-carborane: structural insights and interaction with Cu overlayers

    International Nuclear Information System (INIS)

    X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) are used to investigate the chemical and electronic structure of boron carbide films deposited from ortho-carborane precursors using plasma-enhanced chemical vapor deposition (PECVD), and the reactivity of PECVD films toward sputter-deposited Cu overlayers. The XPS data provide clear evidence of enhanced ortho-carborane reactivity with the substrate, and of extra-icosahedral boron and carbon species; these results differ from results for films formed by condensation and electron beam induced cross-linking of ortho-carborane (EBIC films). The UPS data show that the valence band maximum for PECVD films is ∼1.5 eV closer to the Fermi level than for EBIC films. The XPS data also indicate that PECVD films are resistant to thermally-stimulated diffusion of Cu at temperatures up to 1000 K in UHV, in direct contrast to recently reported results, but important for applications in neutron detection and in microelectronics. (paper)

  20. Blue-shifted emission and enhanced quantum efficiency viaπ-bridge elongation in carbazole-carborane dyads.

    Science.gov (United States)

    Wang, Zhaojin; Jiang, Peng; Wang, Tianyu; Moxey, Graeme J; Cifuentes, Marie P; Zhang, Chi; Humphrey, Mark G

    2016-06-21

    Carbazole-carborane linear dyads and di(carbazole)-carborane V-shaped dyads with phenyleneethynylene-based bridges have been synthesized. The V-shaped dyads display the expected red-shifts in the location of their UV-Vis absorption maxima on bridge-lengthening, but show unusual blue-shifts in charge-transfer (CT) emission on the same π-system lengthening. These blue-shifts can be attributed to the 2n + 3 electron count within the carborane cluster in the excited state. The linear dyads luminesce via a combination of local excited (LE) and CT emission, with a red-shift in LE emission and a blue-shift in CT emission accompanying π-bridge elongation. A quantum efficiency as high as 86% in the solution state is achieved from the hybrid LE/CT emission. Time-dependent density functional theory (TD-DFT) calculations at the excited state of these compounds have clarified the photoluminescence blue-shift and suggested a typical cluster C-C bond elongation in the V-shaped dyads. Calculations on the elongated linear dyads have suggested that the electron density is localized at the phenyleneethynylene-containing bridge. PMID:27225829

  1. Intramolecular hydrogen bonding stabilizes the nuclearity of complexes. A comparative study based on the H-carborane and Me-carborane framework.

    Science.gov (United States)

    Fontanet, Mònica; Rodríguez, Montserrat; Fontrodona, Xavier; Romero, Isabel; Viñas, Clara; Teixidor, Francesc

    2015-06-14

    New dinuclear carboranylcarboxylate-bridged and mononuclear copper(ii) compounds containing the 1-CO2H-2-H-1,2-closo-C2B10H10 carborane ligand () have been synthesized from the previously synthesized dinuclear compound [Cu2(μ-L)4(THF)2], . Reaction of with CuSO4 in THF leads to the dinuclear compound [Cu2(μ-L)4(THF)2], . The reaction of with different terminal pyridyl ligands leads to the formation of a series of structurally analogous complexes by substitution of the terminal ligand THF (Lt = py, ; p-CF3-py, ; p-CH3-py, ), which maintain the structural Cu2(μ-O2CR)4 core in most of the cases except for o-(CH3)2-py where a mononuclear compound () is exclusively obtained. In the case of and , other dinuclear compounds [Cu2(L)4(Lt)4], and are obtained in lower yield. These compounds have been characterized using analytical, spectroscopic (NMR, IR, UV-visible) and electrochemical techniques (CV, DPV). X-ray analysis revealed a paddle-wheel structure for the main dinuclear compounds with a square-pyramidal geometry around each copper ion and the carboranylcarboxylate ions bridging two copper atoms in syn-syn mode. In the case of and there are two carboranylcarboxylate ions bridging the copper atoms in syn-anti mode whereas the other two adopt a monodentate coordination mode. The mononuclear complex obtained with the o-(CH3)-py ligand presents a square-planar structure, in which the carboranylcarboxylate ligand adoptsmonodentate coordination. The effect of the substituent group on the cluster of the carboranylcarboxylate ligands on the reactivity of compound is also discussed. PMID:25974628

  2. The electronic structures and photophysical properties of platinum complexes with C^N^N ligands: the influence of the carborane substituent.

    Science.gov (United States)

    Zhang, Wenting; Luo, Yafei; Xu, Yanyan; Tian, Li; Li, Ming; He, Rongxing; Shen, Wei

    2015-11-01

    Carboranes have attracted increasing interest in the scientific community due to their remarkable structures and strong electron-withdrawing abilities. In this article, four platinum complexes [(C^N^N)PtC[triple bond, length as m-dash]CPh](1), [(C^N^N)PtC[triple bond, length as m-dash]C-TPA](2), [(C^N^N)PtC[triple bond, length as m-dash]C-TAB](3), [(C^N^N)PtC[triple bond, length as m-dash]C-CB](4) (where TPA = triphenylamine, TAB = triarylboryl, CB = o-carborane) have been calculated via density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods to mainly explore the influence of carborane substituents on electronic structures, photophysical properties and radiative decay processes. The calculated results reveal that 2 with electron-donating triphenylamine has a low radiative decay rate constant and a red-shifted emission band, but 3 and 4 containing electron-withdrawing triarylboryl and o-carborane exhibit the opposite properties, especially 4 is supposed to have the highest phosphorescence quantum yield with the smallest nonradiative decay rate constant. These findings successfully illustrated the structure-property relationship and the designed complex 4 with carborane can serve as a highly efficient phosphorescent material in the future. PMID:26419292

  3. Weak C-H acids as protonophores can carry hydrogen ions through lipid membranes and mitochondria: a case of o-carborane.

    Science.gov (United States)

    Rokitskaya, Tatyana I; Khailova, Ljudmila S; Makarenkov, Anton V; Ol'shevskaya, Valentina A; Kalinin, Valery N; Antonenko, Yuri N

    2016-06-28

    ortho-Carborane (1,2-C2B10H12) was found to be a carrier of protons in both mitochondrial and artificial lipid membranes, suggesting that this dicarborane can reversibly release hydrogen ions and diffuse through the membranes in neutral and anionic forms. Similar to conventional uncouplers (e.g. 2,4-dinitrophenol), o-carborane stimulated mitochondrial respiration and decreased the membrane potential at concentrations of tens of micromoles. Protonophoric activity of o-carborane was observed both by a fluorometric assay using pyranine-loaded liposomes and electrical current measurements across planar lipid bilayers. Substantial contribution of the proton flux to the o-carborane-mediated current was proved by a shift of the zero current voltage upon imposing a pH gradient across the membrane. Meta-carborane (1,7-C2B10H12) lacked the protonophoric activity in line with its reduced C-H acidity. The results suggest that weak C-H acids can exhibit protonophoric activity in the biological environment. The finding of a new class of protonophoric compounds is of substantial interest due to promising anti-obesity and anti-diabetic properties of uncouplers. PMID:27265316

  4. Visible-Light-Promoted Photocatalytic B-C Coupling via a Boron-Centered Carboranyl Radical: Facile Synthesis of B(3)-Arylated o-Carboranes.

    Science.gov (United States)

    Zhao, Da; Xie, Zuowei

    2016-02-24

    A visible-light-mediated in situ generation of a boron-centered carboranyl radical (o-C2 B10 H11(.)) has been described. With eosin Y as a photoredox catalyst, 3-diazonium-o-carborane tetrafluoroborate [3-N2-o-C2B10H11][BF4] was converted into the corresponding boron-centered carboranyl radical intermediate, which can undergo efficient electrophilic substitution reaction with a wide range of (hetero)arenes. This general and simple procedure provides a metal-free alternative for the synthesis of 3-(hetero)arylated-o-carboranes. PMID:26822125

  5. Carborane derivatives loaded into liposomes as efficient delivery systems for boron neutron capture therapy.

    Science.gov (United States)

    Altieri, S; Balzi, M; Bortolussi, S; Bruschi, P; Ciani, L; Clerici, A M; Faraoni, P; Ferrari, C; Gadan, M A; Panza, L; Pietrangeli, D; Ricciardi, G; Ristori, S

    2009-12-10

    Boron neutron capture therapy (BNCT) is an anticancer therapy based on the incorporation of (10)B in tumors, followed by neutron irradiation. Recently, the synthesis and delivery of new boronated compounds have been recognized as some of the main challenges in BNCT application. Here, we report on the use of liposomes as carriers for BNCT active compounds. Two carborane derivatives, i.e., o-closocarboranyl beta-lactoside (LCOB) and 1-methyl-o-closocarboranyl-2-hexylthioporphyrazine (H(2)PzCOB), were loaded into liposomes bearing different surface charges. The efficacy of these formulations was tested on model cell cultures, that is, DHD/K12/TRb rat colon carcinoma and B16-F10 murine melanoma. These induce liver and lung metastases, respectively, and are used to study the uptake of standard BNCT drugs, including borophenylalanine (BPA). Boron concentration in treated cells was measured by alpha spectrometry at the TRIGA mark II reactor (University of Pavia). Results showed high performance of the proposed formulations. In particular, the use of cationic liposomes increased the cellular concentration of (10)B by at least 30 times more than that achieved by BPA. PMID:19954249

  6. BODIPY functionalized o-carborane dyads for low-energy photosensitization.

    Science.gov (United States)

    Jin, Guo Fan; Cho, Yang-Jin; Wee, Kyung-Ryang; Hong, Seong Ahn; Suh, Il-Hwan; Son, Ho-Jin; Lee, Jong-Dae; Han, Won-Sik; Cho, Dae Won; Kang, Sang Ook

    2015-02-14

    A new type of organic dyad that can induce low-energy photosensitization has been developed; electron donor and electron acceptor units are boron dipyrromethene (BODIPY) and ortho-carborane (o-Cb), respectively. The new dyads consist of a V-shaped BODIPY-(o-Cb)-BODIPY molecular array in which two BODIPY units are substituted onto two adjacent carbon atoms of the central o-Cb. In the presence of the o-Cb unit, as an electron acceptor, significant fluorescence quenching was observed which indicated that photoinduced electron transfer (PET) had occurred from the end-on BODIPY units to the central o-Cb with PET efficiencies of 63-71%. As a result, the corresponding cationic and anionic species that are responsible for the charge transfer state were detected by the serial spectroelectrochemical studies: cationic BODIPY radicals at 400 nm at the applied voltage of 1.44 V and broad absorption bands of anionic o-Cb radicals in the range of 250-490 nm at -1.84 V. Transient absorption studies further confirmed the BODIPY radical anion at 540 nm and the o-Cb radical anion at 350-475 nm with a structureless broad band. PMID:25482506

  7. Synthesis and in Vitro Studies of a Series of Carborane-Containing Boron Dipyrromethenes (BODIPYs).

    Science.gov (United States)

    Xuan, Sunting; Zhao, Ning; Zhou, Zehua; Fronczek, Frank R; Vicente, M Graça H

    2016-03-10

    A series of seven BODIPYs functionalized with ortho-carborane groups at the 8(meso) or 3/5(α) position were synthesized and characterized by NMR, HRMS, HPLC, and in the cases of 2b and 5b, by X-ray analysis. The BODIPYs exhibited low dark toxicity and phototoxicity toward human glioma T98G cells, and their cellular uptake varied significantly, with 5b accumulating the most and 7 the least. All BODIPYs localized mainly within the cell ER. The BODIPYs showed higher permeabilities than lucifer yellow across human hCMEC/D3 brain endothelial cell monolayers as the BBB model. Among this series, 1b showed the highest BBB permeability (Pe = 16.4 × 10(-5) cm/s), probably as a result of its lower MW (366 Da) and favorable hydrophobicity (log P = 1.5). The combination of low cytotoxicity, amphiphilicity, high boron content, high cellular uptake, and moderate BBB permeability renders these compounds promising boron delivery agents for the BNCT of brain tumors. PMID:26849474

  8. Simplification of electrospray mass spectra of Polysorbate 80 via cation transfer to carborane anions.

    Science.gov (United States)

    Betancourt, Stella K; Pilo, Alice L; Bu, Jiexun; McLuckey, Scott A

    2016-06-01

    Mass spectrometric analysis of polymer mixtures via electrospray ionization can be complicated due the presence of multiple ion types, multiple charge states and multiple oligomeric distributions that complicate the detection and identification of mixture components. Polysorbate 80 (commercially known as Tween(®) 80) provides an example of this type, where the presence of polyoxyethylene sorbitan monooleate (PSO) byproducts gives rise to overlapping polymer distributions. It is desirable to simplify the spectrum in order to identify each component of what is inherently a complex mixture of fatty esters bound to different head groups. In this work, we show that gas-phase ion/ion reactions with carborane anions allow for the charge reduction of Tween(®) 80 peaks by selectively removing metal adducts bound to the synthetic polymer. The resulting singly charged spectrum reduces overlapping distributions and thus simplifies the identification of the components found in a Tween(®) 80 sample. The overall approach described here would likely lead to similar benefits in the analysis of other polymers that tend to ionize via metal ion adduction. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27270869

  9. Electrochemistry of 1-X-12-Y-CB11-Me10 - carborane anions in liquid CO2

    Czech Academy of Sciences Publication Activity Database

    Wahab, Abdul; Stepp, Brian R.; Klíma, Jiří; Michl, Josef; Ludvík, Jiří

    Prague: J. Heyrovský Instotute of Physical Chemistry, v.v.i, 2010 - (Hudská, V.; Ludvík, J.). s. 42 ISBN 978-80-87351-06-2. [The Heyrovský Discussion. Electrochemistry of Organic Molecules and Coordination Compounds /43./. 30.05.2010-03.06.2010, Třešť] R&D Projects: GA MŠk LC510; GA AV ČR IAA400550708 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : electrochemistry * carborane anions Subject RIV: CG - Electrochemistry

  10. Interaction of carboranyl boron-centred radicals with phosphites and addition of carborane-containing and some others phosphoranyl radicals to 3,6-di-tret.butyl-ortho-benzoquinone

    International Nuclear Information System (INIS)

    Reactivity of B-carboranyl radicals in their interaction with phosphites has been studied. It is shown, that preparative photolysis of bis (m-carborane-9-yl) mercury ad bis (p-carborane-2-yl) mercury with trimethylphosphite results in dimethyl esters of m- and p-B-carboranylphosphponic acids. Interaction between carboranyl boron-centred radicals and phosphites proceeds via phosphoranyl radical formation. The difference in reactivity of isomeric B-carboranyl radicals is connected with decrease of attacking radical electronegativity in the series of p- > m- > 0 - carboranes

  11. What is so puzzling about carborane radical? Spin density distribution in CB11(CH3)12 as studied by electron paramagnetic resonance

    Czech Academy of Sciences Publication Activity Database

    Kaleta, Jiří; Tarábek, Ján; Akdag, A.; Pohl, Radek; Michl, Josef

    Brno : Masaryk University, 2014 - (Novotný, J.; Foroutan -Nejad, C.; Marek, R.). C12 ISBN 978-80-86441-45-0. [NMR Valtice. Central European NMR Meeting /29./. 27.4.-30.4.2014, Valtice] Institutional support: RVO:61388963 Keywords : carboranes * radical * EPR * spin density * hyperfine splitting constants Subject RIV: CF - Physical ; Theoretical Chemistry

  12. Dearomative [2 + 2] Cycloaddition and Formal C-H Insertion Reaction of o-Carboryne with Indoles: Synthesis of Carborane-Functionalized Heterocycles.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2015-07-29

    o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized heterocycles. Reaction of o-carboryne with N-protected indoles gave carborane-fused indolines if the protecting group was TMS via dearomative [2 + 2] cycloaddition or carboranyl indoles for N-alkyl ones through formal C-H insertion reaction. For N-aryl indoles, both reactions were observed, giving two products, in which the product ratio was dependent upon the nature of the substituents on the aryl rings. In general, electron-withdrawing substituents favor [2 + 2] cycloaddition, whereas electron-donating substituents promote a formal C-H insertion pathway. This reaction is also compatible with other heteroaromatics. Thus, a stepwise reaction mechanism was proposed to account for the experimental observations. These protocols offer general and efficient methods for the preparation of carborane-functionalized indoles and indolines as well as other heterocycles. The observed dearomative [2 + 2] cycloaddition represents the first example of indoles to undergo such reaction in the absence of transition metals or without UV irradiation. All new compounds were fully characterized by (1)H, (13)C, and (11)B NMR spectroscopy as well as HRMS spectrometry. Some were further confirmed by single-crystal X-ray analyses. PMID:26160111

  13. Effect of meta-carborane on segmental dynamics in a bimodal Poly(dimethylsiloxane) network

    Energy Technology Data Exchange (ETDEWEB)

    Lewicki, J; Maxwell, R S; Patel, M; Herberg, J; Swain, A C; Liggat, J; Pethrick, R

    2008-06-11

    Bimodal networks of polydimethylsiloxane (PDMS) filled with varying amounts of icosahedral meta-carborane (m-CB) have been developed and characterized by broadband dielectric spectroscopy (BDS) and static {sup 1}H Multiple Quantum Nuclear Magnetic Resonance (MQ NMR). Both BDS and MQ NMR showed evidence for a decrease in the polymer chain dynamics. BDS spectra quantified a normal-mode relaxation near 40 Hz at 40 C. The frequency maximum observed for filled samples decreased with increasing m-CB content until contents greater than 5 wt. %. The width of the relaxation spectrum increased with the addition of small quantities of filler and decreased with filler contents greater that 5 wt. %. Agglomeration effects were observed at loadings greater than 5 wt % as manifest by the onset of low frequency Maxwell-Wagner-Sillars (MWS) processes. The MQ NMR data allowed the characterization of distributions of the residual dipolar couplings, <{Omega}{sub d}> and thus in the dynamic order parameter, Sb, consistent with the bimodal network architecture expected from the synthesis protocol used. Upon addition of less than 10 wt.% m-CB filler, the mean <{Omega}{sub d}> for the longer chains increased by 46% and the width of the distribution increased by 33%. The mean <{Omega}{sub d}> for the shorter chains increased by much less, indicative of preferential dispersion of the filler particles in the long chain domains of the network structure. We conclude that the mechanism of reinforcement is likely a free volume space filling at low loadings transitioning to complex molecular filler and polymer chain interaction phenomena at higher loadings.

  14. Site-specific electron-induced cross-linking of ortho-carborane to form semiconducting boron carbide

    Energy Technology Data Exchange (ETDEWEB)

    Pasquale, Frank L. [Department of Chemistry, University of North Texas, Denton, TX 76203 (United States); Kelber, Jeffry A., E-mail: kelber@unt.edu [Department of Chemistry, University of North Texas, Denton, TX 76203 (United States)

    2012-01-15

    Semiconducting boron carbide (B{sub 10}C{sub 2}H{sub x}) films have been formed by bombardment of condensed ortho-carborane (closo-1,2-dicarbadodecaborane) multilayers on polycrystalline copper substrates by 200 eV electrons under ultra-high vacuum conditions. The film formation process was characterized by X-ray and ultraviolet photoelectron spectroscopies. Electron bombardment results in the cross-linking of the icosahedral units. The cross-linking is accompanied by a shift in the B(1s) binding energy indicating site-specific cross-linking between two boron sites on adjacent carborane icosahedra. An additional shift in valence band binding energies attributed to the surface photovoltage effect is indicative of the formation of a p-type semiconductor. This is the first report of B{sub 10}C{sub 2}H{sub x} formation by electron bombardment of condensed films, and the data indicate that this method is a viable route towards formation of ultra-thin films of tailored composition and cross-linkages for emerging nanoelectronics and sensor applications.

  15. Aggregation-induced emission of diarylamino-π-carborane triads: effects of charge transfer and π-conjugation.

    Science.gov (United States)

    Cho, Yang-Jin; Kim, So-Yoen; Cho, Minji; Han, Won-Sik; Son, Ho-Jin; Cho, Dae Won; Kang, Sang Ook

    2016-04-14

    Carborane-based donor-π-acceptor triads (D-π-A-π-D) bearing triarylamine moieties were synthesised. All the monomeric triads showed a blue-green emission in a dilute solution, which was assigned as an intramolecular charge-transfer (CT) emission. The intramolecular CT emission showed large Stokes shifts at a higher solvent polarity. The intramolecular CT emission further shifted to a longer wavelength with the increase in π-conjugation. Interestingly, a strong red emission was observed in highly concentrated solutions or in the solid state, which was assigned as an aggregation-induced emission (AIE). Moreover, the AIE strongly depended on solvent polarity. A large Stokes shift in AIE was attributed to the strong CT character. The changes in the dipole moment for the AIE state and monomer emission were evaluated using the Lippert-Mataga relationship. The density functional theory calculations showed that the change in electron distribution between the aryl amino group (highest occupied molecular orbital, HOMO) and the carborane moiety (lowest unoccupied molecular orbital, LUMO) indicates the intramolecular CT character, and the emission colour changes were attributed to the HOMO-LUMO energy gap controlled by the π-extension of the phenylene linker. The electrochemical properties such as oxidation and reduction potentials were consistent with theoretical calculation results. The emission properties were affected by two main factors: solvent polarity and solubility. PMID:26996491

  16. Synthesis and biological evaluation of novel m-carborane-containing estrogen receptor partial agonists as SERM candidates.

    Science.gov (United States)

    Ohta, Kiminori; Ogawa, Takumi; Kaise, Asako; Endo, Yasuyuki

    2015-08-15

    We designed and synthesized novel m-carborane-containing selective estrogen receptor modulator (SERM) candidates using previously reported m-carborane-containing ER partial agonist 1 as the lead compound. Biological activities were evaluated by means of ERα competitive binding assay and MCF-7 cell proliferation assay. Re-positioning the N,N-dimethylaminoethyloxy group at the para position of 1 to the meta position enhanced the ERα-binding affinity, and 4c showed the highest relative binding affinity (RBA: 83 vs 17β-estradiol = 100) among the tested compounds. Compound 4b showed the most potent ER-agonist activity (EC50: 1.4 nM) and the lowest maximal efficacy (Emax: 50%) in MCF-7 cell proliferation assay. Inhibition of 0.1 nM 17β-estradiol-induced MCF-7 cell proliferation by 4b (IC50: 0.4 μM) was at least 10 times more potent than that of the lead compound 1. PMID:26077489

  17. Synthesis and structural characterization of 14-vertex germa-, stanna-, and plumba-carboranes.

    Science.gov (United States)

    Zheng, Fangrui; Xie, Zuowei

    2014-04-01

    This article reports the synthesis and structures of several 14-vertex germa-, stanna-, and plumba-carboranes of the MC2B11 system. The reaction of GeCl2·dioxane, SnCl2 or Pb(OAc)2 with [8,9-(CH2)3-8,9-C2B11H11][Na2] in THF gave, after recrystallization from bidentate ligands such as bipyridine, 4,4'-dimethyl-2,2'-bipyridine, phenantroline and 1,2-bis(diphenylphosphino)ethane (dppe), eight 14-vertex p-block metallacarboranes 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-GeC2B11H11 (1), 2,3-(CH2)3-1-(4',4''-dimethyl-bipyridine)-1,2,3-GeC2B11H11 (2), 2,3-(CH2)3-1-(1',10'-phenantroline)-1,2,3-GeC2B11H11 (3), 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-SnC2B11H11 (4), 2,3-(CH2)3-1-(4',4''-dimethyl-bipyridine)-1,2,3-SnC2B11H11 (5), 2,3-(CH2)3-1-(1',10'-phenantroline)-1,2,3-SnC2B11H11 (6), 2,3-(CH2)3-1-(dppe)-1,2,3-SnC2B11H11 (7) and 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-PbC2B11H11 (8) in high isolated yields. Single-crystal X-ray analyses reveal that they adopt a distorted-bicapped-hexagonal antiprism geometry, in which the p-block metal atom slips away from the above center of the C2B4 bonding face towards the boron side, leading to an η(4) bonding mode. The results suggest that [nido-8,9-(CH2)3-8,9-C2B11H11](2-) is a redox inactive species and a good π-ligand for transition metals and p-block elements. PMID:24162337

  18. Nanoscaled carborane ruthenium(II-arene complex inducing lung cancer cells apoptosis

    Directory of Open Access Journals (Sweden)

    Yan Hong

    2011-02-01

    Full Text Available Abstract Background The new ruthenium(II-arene complex, which bearing a carborane unit, ruthenium and ferrocenyl functional groups, has a novel versatile synthetic chemistry and unique properties of the respective material at the nanoscale level. The ruthenium(II-arene complex shows significant cytotoxicity to cancer cells and tumor-inhibiting properties. However, ruthenium(II-arene complex of mechanism of anticancer activity are scarcely explored. Therefore, it is necessary to explore ruthenium(II-arene complex mechanism of anticancer activity for application in this area. Results In this study, the ruthenium(II-arene complex could significantly induce apoptosis in human lung cancer HCC827 cell line. At the concentration range of 5 μM-100 μM, ruthenium(II-arene complex had obvious cell cytotoxicity effect on HCC827 cells with IC50 values ranging 19.6 ± 5.3 μM. Additionally, our observations demonstrate that the ruthenium(II-arene complex can readily induce apoptosis in HCC827 cells, as evidenced by Annexin-V-FITC, nuclear fragmentation as well as DNA fragmentation. Treatment of HCC827 cells with the ruthenium(II-arene complex resulted in dose-dependent cell apoptosis as indicated by high cleaved Caspase-8,9 ratio. Besides ruthenium(II-arene complex caused a rapid induction of cleaved Caspase-3 activity and stimulated proteolytic cleavage of poly-(ADP-ribose polymerase (PARP in vitro and in vivo. Conclusion In this study, the ruthenium(II-arene complex could significantly induce apoptosis in human lung cancer HCC827 cell line. Treatment of HCC827 cells with the ruthenium(II-arene complex resulted in dose-dependent cell apoptosis as indicated by high cleaved Caspase-8,9 ratio. Besides ruthenium(II-arene complex caused a rapid induction of cleaved Caspase-3 activity and stimulated proteolytic cleavage of poly-(ADP-ribose polymerase (PARP in vitro and in vivo. Our results suggest that ruthenium(II-arene complex could be a candidate for further

  19. Direct astatination of a tumour-binding protein, human epidermal growth factor, using nido-carborane as a prosthetic group

    International Nuclear Information System (INIS)

    A method for direct astatine labeling of proteins has been investigated. Binding sites for astatine were created by coupling of a nido-carborane derivative to a protein, the human epidermal growth factor (hEGF), using two different conjugation methods - by glutaraldehyde cross-linking or by introduction of sulfohydryl groups by Traut's reagent with subsequent linking of ANC-1 with m-maleimidobenzoyl-N-hydroxysulfosuccinimide ester. The conjugates were astatinated using the Chloramine-T method in high yield. The best labeling was obtained by the glutaraldehyde conjugate with an average yield of 68 ± 9%. In vitro stability tests indicated that the glutaraldehyde conjugated label was as stable as hEGF labeled with astatobenzoate. (author)

  20. Hot wire chemical vapour deposition (HWCVD) of boron carbide thin films from ortho-carborane for neutron detection application

    International Nuclear Information System (INIS)

    Detection of neutrons is possible if suitable converters such as Li, LiF or 10B in the form of thin films are used along with the semiconductor device. The use of boron (10B) in some host matrix as a neutron detector is attractive due to its large neutron capture cross-section. Boron carbide (BC) films are deposited on silicon substrates by HWCVD technique using solid ortho-carborane (o-C2B10H12) precursor with argon as carrier gas. The films contain 10B required for neutron detection as confirmed by the Secondary Ion Mass Spectroscopy. Variations in its structure as well as the chemical bonding configurations using Fourier Transform Infra-Red, Raman and X-ray diffraction spectroscopy have been studied.

  1. Synthesis of a Neutral Mixed-Valence Diferrocenyl Carborane for Molecular Quantum-Dot Cellular Automata Applications.

    Science.gov (United States)

    Christie, John A; Forrest, Ryan P; Corcelli, Steven A; Wasio, Natalie A; Quardokus, Rebecca C; Brown, Ryan; Kandel, S Alex; Lu, Yuhui; Lent, Craig S; Henderson, Kenneth W

    2015-12-14

    The preparation of 7-Fc(+) -8-Fc-7,8-nido-[C2 B9 H10 ](-) (Fc(+) FcC2 B9 (-) ) demonstrates the successful incorporation of a carborane cage as an internal counteranion bridging between ferrocene and ferrocenium units. This neutral mixed-valence Fe(II) /Fe(III) complex overcomes the proximal electronic bias imposed by external counterions, a practical limitation in the use of molecular switches. A combination of UV/Vis-NIR spectroscopic and TD-DFT computational studies indicate that electron transfer within Fc(+) FcC2 B9 (-) is achieved through a bridge-mediated mechanism. This electronic framework therefore provides the possibility of an all-neutral null state, a key requirement for the implementation of quantum-dot cellular automata (QCA) molecular computing. The adhesion, ordering, and characterization of Fc(+) FcC2 B9 (-) on Au(111) has been observed by scanning tunneling microscopy. PMID:26516063

  2. Carborane-Based Carbonic Anhydrase Inhibitors: Insight into CAII/CAIX Specificity from a High-Resolution Crystal Structure, Modeling, and Quantum Chemical Calculations

    Directory of Open Access Journals (Sweden)

    Pavel Mader

    2014-01-01

    Full Text Available Carborane-based compounds are promising lead structures for development of inhibitors of carbonic anhydrases (CAs. Here, we report structural and computational analysis applicable to structure-based design of carborane compounds with selectivity toward the cancer-specific CAIX isoenzyme. We determined the crystal structure of CAII in complex with 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane at 1.0 Å resolution and used this structure to model the 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane interactions with CAIX. A virtual glycine scan revealed the contributions of individual residues to the energy of binding of 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane to CAII and CAIX, respectively.

  3. Carborane-Based Carbonic Anhydrase Inhibitors: Insight into CAII/CAIX Specificity from a High-Resolution Crystal Structure, Modeling, and Quantum Chemical Calculations

    Science.gov (United States)

    Mader, Pavel; Pecina, Adam; Cígler, Petr; Lepšík, Martin; Šícha, Václav; Hobza, Pavel; Grüner, Bohumír; Fanfrlík, Jindřich; Brynda, Jiří; Řezáčová, Pavlína

    2014-01-01

    Carborane-based compounds are promising lead structures for development of inhibitors of carbonic anhydrases (CAs). Here, we report structural and computational analysis applicable to structure-based design of carborane compounds with selectivity toward the cancer-specific CAIX isoenzyme. We determined the crystal structure of CAII in complex with 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane at 1.0 Å resolution and used this structure to model the 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane interactions with CAIX. A virtual glycine scan revealed the contributions of individual residues to the energy of binding of 1-methylenesulfamide-1,2-dicarba-closo-dodecaborane to CAII and CAIX, respectively. PMID:25309911

  4. Boron Clusters as a Platform for New Materials: Synthesis of Functionalized o-Carborane (C2 B10 H12 ) Derivatives Incorporating DNA Fragments.

    Science.gov (United States)

    Janczak, Slawomir; Olejniczak, Agnieszka; Balabańska, Sandra; Chmielewski, Marcin K; Lupu, Marius; Viñas, Clara; Lesnikowski, Zbigniew J

    2015-10-19

    A synthetic strategy for functionalization of the three vertices of o-carborane and the attachment of the obtained triped to the solid support was developed. Further functionalization of the triped with short DNA sequences by automated DNA synthesis was achieved. The proposed methodology is a first example of boron cluster chemistry on a solid support opening new perspectives in boron cluster functionalization. PMID:26346614

  5. Physisorbed o-carborane onto lyso-phosphatidylcholine-functionalized, single-walled carbon nanotubes: a potential carrier system for the therapeutic delivery of boron

    Energy Technology Data Exchange (ETDEWEB)

    Yannopoulos, S N; Bouropoulos, N [Foundation for Research and Technology, Hellas-Institute of Chemical Engineering and High Temperature Chemical Processes-FORTH/ICE-HT, PO Box 1414, GR-26504 Patras (Greece); Zouganelis, G D [School of Biological Sciences, University of Portsmouth, St Michael' s Building, White Swan Road, Portsmouth PO1 2DT (United Kingdom); Nurmohamed, S; Smith, J R; Fatouros, D G; Tsibouklis, J [School of Pharmacy and Biomedical Sciences, University of Portsmouth, St Michael' s Building, White Swan Road, Portsmouth PO1 2DT (United Kingdom); Calabrese, G, E-mail: sny@iceht.forth.gr, E-mail: dimitris.fatouros@port.ac.uk [School of Pharmacy and Chemistry, Kingston University, Penrhyn Road, Kingston upon Thames, Surrey, KT1 2EE (United Kingdom)

    2010-02-26

    A combination of data from ICP-MS, Raman spectroscopy, UV-vis spectrometry, atomic force microscopy, {zeta}-potential measurements and gel electorphoresis studies has shown that o-carborane may be immobilized on stable aqueous dispersions of lyso-phosphatidylcholine-functionalized single-walled carbon nanotubes, which in turn indicates the potential of such structures for deployment as carrier vehicles in boron neutron capture therapy.

  6. Droplet electrochemical study of the pH dependent redox behavior of novel ferrocenyl-carborane derivatives and its application in specific cancer cell recognition

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Changyu [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Laboratory), Southeast University, Nanjing 210096 (China); Shah, Afzal [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Ye, Hongde [State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093 (China); Chen, Xiao; Ye, Jing; Jiang, Hui [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Laboratory), Southeast University, Nanjing 210096 (China); Chen, Baoan [Department of Hematology, the Affiliated Zhongda Hospital, Clinical Medical School, Southeast University, Nanjing 210009 (China); Wang, Xuemei, E-mail: xuewang@seu.edu.cn [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Laboratory), Southeast University, Nanjing 210096 (China); Yan, Hong, E-mail: hyan1965@nju.edu.cn [State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093 (China)

    2015-02-01

    Highlights: • Electrochemical behaviors of novel ferrocenyl based carboranes (FcCB) were explored with a droplet system. • The shifts of peak potentials with changes of pH values indicated the involvement of proton during electron transfer reaction. • Normal cells and cancer cells could be specifically recognized by using FcCB as probe. • This electrochemical method in a droplet shows great potential application for relevant diagnostics of clinical samples. - Abstract: Novel ferrocenyl based carboranes (FcCBs) and their distinguish behavior for cancer cell recognition have been explored in this contribution. The voltammetric study in a droplet of 10 μL placed on the surface of a glassy carbon electrode demonstrates the excellent electrochemical behavior of FcCBs, which could be further exploited for establishing the promising and sensitive biosensors. The FcCBs’ redox behavior is examined in a wide pH range, and square wave voltammetry revealed the reversible and irreversible nature of first and second anodic peaks. The obvious shifts in peak potentials corresponding with the change of pH values demonstrate the abstraction of electrons to be accompanied with the transfer of protons. By using the droplet electrochemical technique, FcCBs can be employed to distinguish normal and cancer cells with a linear range from 1.0 × 10{sup 3} to 3.0 × 10{sup 4} cells mL{sup −1} and the limit of detection at 800 cells mL{sup −1}. The novel carborane derivatives could be utilized as important potential molecular probes for specific recognition of cancer cells like leukemia cells from normal cells.

  7. Droplet electrochemical study of the pH dependent redox behavior of novel ferrocenyl-carborane derivatives and its application in specific cancer cell recognition

    International Nuclear Information System (INIS)

    Highlights: • Electrochemical behaviors of novel ferrocenyl based carboranes (FcCB) were explored with a droplet system. • The shifts of peak potentials with changes of pH values indicated the involvement of proton during electron transfer reaction. • Normal cells and cancer cells could be specifically recognized by using FcCB as probe. • This electrochemical method in a droplet shows great potential application for relevant diagnostics of clinical samples. - Abstract: Novel ferrocenyl based carboranes (FcCBs) and their distinguish behavior for cancer cell recognition have been explored in this contribution. The voltammetric study in a droplet of 10 μL placed on the surface of a glassy carbon electrode demonstrates the excellent electrochemical behavior of FcCBs, which could be further exploited for establishing the promising and sensitive biosensors. The FcCBs’ redox behavior is examined in a wide pH range, and square wave voltammetry revealed the reversible and irreversible nature of first and second anodic peaks. The obvious shifts in peak potentials corresponding with the change of pH values demonstrate the abstraction of electrons to be accompanied with the transfer of protons. By using the droplet electrochemical technique, FcCBs can be employed to distinguish normal and cancer cells with a linear range from 1.0 × 103 to 3.0 × 104 cells mL−1 and the limit of detection at 800 cells mL−1. The novel carborane derivatives could be utilized as important potential molecular probes for specific recognition of cancer cells like leukemia cells from normal cells

  8. BA321, a novel carborane analog that binds to androgen and estrogen receptors, acts as a new selective androgen receptor modulator of bone in male mice.

    Science.gov (United States)

    Watanabe, Kenta; Hirata, Michiko; Tominari, Tsukasa; Matsumoto, Chiho; Endo, Yasuyuki; Murphy, Gillian; Nagase, Hideaki; Inada, Masaki; Miyaura, Chisato

    2016-09-01

    Carboranes are a class of carbon-containing polyhedral boron cluster compounds with globular geometry and hydrophobic surface that interact with hormone receptors such as estrogen receptor (ER) and androgen receptor (AR). We have synthesized BA321, a novel carborane compound, which binds to AR. We found here that it also binds to ERs, ERα and ERβ. In orchidectomized (ORX) mice, femoral bone mass was markedly reduced due to androgen deficiency and BA321 restored bone loss in the male, whilst the decreased weight of seminal vesicle in ORX mice was not recovered by administration of BA321. In female mice, BA321 acts as a pure estrogen agonist, and restored both the loss of bone mass and uterine atrophy due to estrogen deficiency in ovariectomized (OVX) mice. In bone tissues, the trabecular bone loss occurred in both ORX and OVX mice, and BA321 completely restored the trabecular bone loss in both sexes. Cortical bone loss occurred in ORX mice but not in OVX mice, and BA321 clearly restored cortical bone loss due to androgen deficiency in ORX mice. Therefore, BA321 is a novel selective androgen receptor modulator (SARM) that may offer a new therapy option for osteoporosis in the male. PMID:27402268

  9. PECVD deposition of a-B/C on Si using a surface-ECR plasma source and O-carborane precursor gas

    International Nuclear Information System (INIS)

    Vacuum wall deposition of a-B/C films has had tremendous positive impact on the performance of tokamak fusion reactors. In the present work, sublimed gas from o-carborane and helium carrier gas are used to create a plasma using the surface-ECR source. The plasma operates in a pressure range of 5 to 15 mTorr and typical flow rates are 5 sccm He plus 0.5--1 sccm o-carborane vapor. The film deposition rate is approximately 200 angstrom/minute. Microwave power levels range 200--500 W at 2.45 GHz. The authors present data from the deposition plasma, including Langmuir probe measurements and time-of-flight (TOF) analyzer measurements of elemental and molecular ion species concentrations. Plasma electron densities on the order of ne = 1011cm-3 and electron temperatures of Te ∼ 2eV were measured. Using these measurements a self-consistent plasma equilibrium is being modeled. The films have been analyzed for atomic constituency using XPS. Thickness is measured by profilometry. Preliminary x-ray diffraction analysis has been performed. Films with a thickness of a few thousand angstrom are routinely obtained

  10. Luminescent properties and structure of multicomponent naphthalene-{beta}-cyclodextrin complexes. 1. Effect of adding third parties, o-carborane or/and adamantane

    Energy Technology Data Exchange (ETDEWEB)

    Nazarov, Valery B. [Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432 Moscow region, Chernogolovka (Russian Federation); Avakyan, Vitaly G., E-mail: avak@photonics.ru [Photochemistry Center of Russian Academy of Sciences, 119421 Moscow, Novatorov 7a (Russian Federation); Rudyak, Vladimir Y.; Alfimov, Michail V. [Photochemistry Center of Russian Academy of Sciences, 119421 Moscow, Novatorov 7a (Russian Federation); Vershinnikova, Tatiana G. [Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432 Moscow region, Chernogolovka (Russian Federation)

    2011-09-15

    Luminescence spectra of water solution of {beta}-cyclodextrin ({beta}-CD) inclusion complexes with naphthalene have been studied in the presence of carcass compounds (CC), adamantane and ocarborane, added in solution as the third parties. It was observed that the CC structure completely determines luminescence type displayed by the three-component complex. Adding adamantane to the solution leads to the disappearance of the spontaneous excimer fluorescence observed usually along with a monomer fluorescence of naphthalene and the appearance of the long lived phosphorescence at room temperature. At the same time, introducing o-carborane in solution of {beta}-CD inclusion complexes with naphthalene results in the dramatic growth of intensity of the excimer band at the expense of lowering intensity of monomer fluorescence. These phenomena were explained using results of the quantum-chemical calculation of the structure and complexation energies at the semi-empirical PM3 and DFT levels of theory. - Highlights: > Structure of carcass compounds determines luminescence types for naphthalene - betaCD complex. > Adding o-carborane leads to the growth of excimer fluorescence at low naphthalene concentrations. > Adding adamantane leads to the room temperature phosphorescence without deoxygenation.

  11. New type of nido-carborane of platinum: a pseudocloso-carborane. X-ray structural investigation of (Ph/sub 3/P)/sub 2/Pt-6,9-C/sub 2/B/sub 8/H/sub 10/

    Energy Technology Data Exchange (ETDEWEB)

    Kukina, G.A.; Porai-Koshits, M.A.; Sergienko, V.S.

    1987-02-01

    The reaction of Na/sub 2/C/sub 2/B/sub 8/H/sub 10/ with Pt(PPh/sub 3/)/sub 2/Cl/sub 2/ gives the complex (Ph/sub 3/P)/sub 2/PtC/sub 2/B/sub 8/H/sub 10/. Its structure has been established by x-ray diffraction analysis /lambdaMo, 6139 reflections, combination of anisotropic and isotropic (C(Ph)) least-squares methods with inclusion of located H(carborane) and calculated H(Ph) atoms, R = 0.045/. The crystals are triclinic: a = 11.035, b = 11.420, c = 16.154 A, ..cap alpha.. = 90.97, ..beta.. = 92.89, ..gamma.. = 114.36/sup 0/, Z = 2, space group P anti 1. It has been shown that the metallocarborane part of the complex has the form of a decarborane basket with C atoms at opposing vertices (6,9) of the outer hexagonal frame and C-Pt-C bonds forming the handle of the basket. All the H atoms of the carborane are terminal, and there is one for each C and B atom. The coordination of the Pt atom is brought up to square coordination by the two P atoms of the phosphine groups. The bond lengths and angles are: Pt-P = 2.297 and 2.322, Pt-C = 2.141 and 2.154 A, PPtP = 93.72, CPtC = 94.8, PPtC = 84.0 and 87.7/sup 0/. The uniqueness of the pseudocloso-type structure found for carborane complexes of Pt and Pd has been noted.

  12. Homoleptic Tris-Cyclometalated Iridium Complexes with Substituted o-Carboranes: Green Phosphorescent Emitters for Highly Efficient Solution-Processed Organic Light-Emitting Diodes.

    Science.gov (United States)

    Kim, Yejin; Park, Sunghee; Lee, Young Hoon; Jung, Jaehoon; Yoo, Seunghyup; Lee, Min Hyung

    2016-01-19

    Homoleptic tris-cyclometalated iridium complexes, fac-Ir[5-(2-RCB)ppy]3 (3a-3c; CB = o-carboran-1-yl; ppy = 2-phenylpyridinato-C(2),N; R = H (3a), Me (3b), (i)Bu (3c)) with 2-R-substituted o-carboranes at the 5-position of the ppy ligand, were prepared and characterized. X-ray diffraction analysis of 3a and 3c revealed that the three C^N ligands adopt a fac-arrangement around the Ir atom and that the carboranyl C-C bond distance increases with increasing steric effects of the 2-R substituent. The phosphorescence wavelengths of the complexes were apparently blue-shifted by ca. 20 nm (λem = 487-493 nm) compared to that of the parent fac-Ir(ppy)3 (4; λem = 508 nm). In particular, 3a-3c were highly emissive in toluene, and the phosphorescence quantum efficiencies of 3a and 3b (ΦPL = 0.95-0.98) were comparable to that of 4. Solution-processed electroluminescent devices incorporating 3a-3c as emitters displayed green light with high performance, and devices based on the 3c dopant showed the highest performance. In particular, the devices based on 3c exhibited performance more than double of that of the device based on 4 in terms of current efficiency (29.6 cd/A for 3c vs 15.8 cd/A for 4 at 4 wt % Ir and 1000 cd/m(2)), power efficiency (11.0 lm/W for 3c vs 6.3 lm/W for 4), and external quantum efficiency (10.2% for 3c vs 4.7% for 4) over a wide range of luminance. The higher PL quantum yields of doped host films with 3c than those with 4 at high dopant concentrations above 8 wt % suggested that along with high phosphorescence quantum efficiency, the steric bulkiness of the 2-(i)Bu-substituted o-carborane in 3c plays a crucial role in improving device performance. PMID:26741792

  13. Crystal Structures of the Carborane Dianions [1,4-(PhCB10H10C)2C6H4]2− and [1,4-(PhCB10H10C)2C6F4]2− and the Stabilizing Role of the para-Phenylene Unit on 2 n+3 Skeletal Electron Clusters**

    Science.gov (United States)

    Kahlert, Jan; Stammler, Hans-Georg; Neumann, Beate; Harder, Rachel A; Weber, Lothar; Fox, Mark A

    2014-01-01

    While carboranes with 2 n+2 and 2 n+4 (n=number of skeletal atoms) skeletal electrons (SE) are widely known, little has been reported on carboranes with odd SE numbers. Electrochemical measurements on two-cage assemblies, where two C-phenyl-ortho-carboranyl groups are linked by a para-phenylene or a para-tetrafluorophenylene bridge, revealed two well separated and reversible two-electron reduction waves indicating formation of stable dianions and tetraanions. The salts of the dianions were isolated by reduction with sodium metal and their unusual structures were determined by X-ray crystallography. The diamagnetic dianions contain two 2 n+3 SE clusters where each cluster has a notably long carborane C–carborane C distance of ca 2.4 Å. The π conjugation within the phenylene bridge plays an important role in the stabilization of these carboranes with odd SE counts. PMID:24574170

  14. A racemic and enantiopure unsymmetric diiron(III) complex with a chiral o-carborane-based pyridylalcohol ligand: combined chiroptical, magnetic, and nonlinear optical properties.

    Science.gov (United States)

    Di Salvo, Florencia; Tsang, Min Ying; Teixidor, Francesc; Viñas, Clara; Planas, José Giner; Crassous, Jeanne; Vanthuyne, Nicolas; Aliaga-Alcalde, Núria; Ruiz, Eliseo; Coquerel, Gerard; Clevers, Simon; Dupray, Valerie; Choquesillo-Lazarte, Duane; Light, Mark E; Hursthouse, Michael B

    2014-01-20

    The design of molecule-based systems combining magnetic, chiroptical and second-order optical nonlinear properties is still very rare. We report an unusually unsymmetric diiron(III) complex 1, in which three bulky chiral carboranylpyridinealkoxide ligands (oCBhmp(-)) bridge both metal ions and the complex shows the above-mentioned properties. The introduction of o-carborane into the 2-(hydroxymethyl)pyridine (hmpH) architecture significantly alters the coordination of the simple or aryl-substituted 2-hmpH. The unusual architecture observed in 1 seems to be triggered by the poor nucleophilicity of our alkoxide ligand (oCBhmp(-)). A very rare case of spontaneous resolution takes place on precipitation or exposure to solvent vapor for the bulk compound, as confirmed by a combination of single-crystal and powder X-ray diffraction, second-harmonic generation, and circular dichroism. The corresponding enantiopure complexes (+)1 and (-)1 have also been synthesized and fully characterized. This research provides a new building block with unique geometry and electronics to construct coordination complexes with multifunctional properties. PMID:24338928

  15. Unprecedented flexibility of the 1,1'-bis(o-carborane) ligand: catalytically-active species stabilised by B-agostic B-H⇀Ru interactions.

    Science.gov (United States)

    Riley, Laura E; Chan, Antony P Y; Taylor, James; Man, Wing Y; Ellis, David; Rosair, Georgina M; Welch, Alan J; Sivaev, Igor B

    2016-01-21

    Doubly-deprotonated 1,1'-bis(o-carborane) reacts with [RuCl2(p-cymene)]2 to afford [Ru(κ3-2,2',3'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(p-cymene)] (1) in which 1,1'-bis(o-carborane) acts as an X2-(C,C')L ligand where "L" is a B3'–H3'⇀Ru B-agostic interaction, fluctional over four BH units (3', 6', 3 and 6)at 298 K but partially arrested at 203 K (B3' and B6'). This interaction is readily cleaved by CO affording [Ru-(κ2-2,2'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(p-cymene)(CO)] (2) with the 1,1'-bis(o-carborane)simply an X2(C,C') ligand. With PPh3 or dppe 1 yields [Ru(κ3-2,3',3-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(PPh3)2] (3) or [Ru(κ3-2,3',3-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(dppe)] (4)via unusually facile loss of the η-(p-cymene) ligand. In 3 and 4 the 1,1'-bis(o-carborane) has unexpectedly transformed into an X2(C,B')L ligand with "L" now a B3–H3⇀Ru B-agostic bond. Unlike in 1 the B-agostic bonding in 3 and 4 appears non-fluctional at 298 K. With CO the B-agostic interaction of 3 is cleaved and a PPh3 ligand is lost to afford [Ru(κ2-2,3'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(CO)3(PPh3)](5), which exists as a 1 : 1 mixture of isomers, one having PPh3 trans to C2, the other trans to B3'. With MeCN the analogous product [Ru(κ2-2,3'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(MeCN)3(PPh3)] (6) is formed as only the former isomer. With CO 4 affords [Ru(κ2-2,3'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(CO)2(dppe)] (7), whilst with MeCN 4 yields [Ru(κ2-2,3'-{1-(1'-1',2'-closo-C2B10H10)-1,2-closo-C2B10H10})(MeCN)2(dppe)] (8). In 5 and 6 the three common ligands (CO or MeCN)are meridional, whilst in 7 and 8 the two monodentate ligands are mutually trans. Compound 1 is an 18-e,6-co-ordinate, species but with a labile B-agostic interaction and 3 and 4 are 16-e, formally 5-co-ordinate,species also including a B-agostic interaction, and thus all three have the potential to act as

  16. Synthesis, relaxation properties and in vivo assessment of a carborane-GdDOTA-monoamide conjugate as an MRI blood pool contrast agent.

    Science.gov (United States)

    Goswami, Lalit N; Cai, Quanyu; Ma, Lixin; Jalisatgi, Satish S; Hawthorne, M Frederick

    2015-09-01

    The synthesis, relaxivity measurements and in vivo assessment of a carborane-GdDOTA-monoamide (CB-GdDOTA-MA) amphiphilic conjugate as a blood pool contrast agent (BPCA) is reported. This BPCA exhibited excellent binding (87.4%) with human serum albumin (HSA) and showed a higher relaxivity value (r1 = 6.8 mM(-1) s(-1), 7 T) as compared to the clinically used BPCA, MS-325 (r1 = 5.1 mM(-1) s(-1), 9.4 T) in PBS. The blood pool contrast enhancement (CE) capability of CB-GdDOTA-MA was evaluated by performing MR angiography (MRA) in CF1 mice (n = 4) at a Gd dose of 0.1 mmol per kg body weight. The significant CE of blood vessels persisted for about 3-4 min post-injection (p.i.) and quickly diminishes over time. The significant CE of the bladder for up to 3 h p.i. indicated that the renal system is the primary clearance pathway for CB-GdDOTA-MA. However, the CE of liver tissues and intestine (up to 24 h p.i.) is suggestive of a significant hepatic uptake of the CB-GdDOTA-MA. PMID:26204958

  17. Nature of weak inter- and intramolecular interactions in crystals. Communication 5. Interactions Na...H-B in a crystal of sodium salt of charge compensated nido-carborane [9-SMe2-7,8-C2B9H10]-

    International Nuclear Information System (INIS)

    The character of electron density distribution in the C2B3 open face, the influence of the SMe2 group on the character of electron density distribution, and the nature of the sodium-anion interaction were studied based on the data of high-resolution X-ray diffraction study of crystals of the sodium salt of charge-compensated nido-carborane [9-SMe2-7,8- C2B9H10]- and quantum-chemical calculations for the Na...H-B-bonded dimer, the isolated [9-SMe2-7,8-C2B9H10]- anion, and the [7,8-C2B9H10]2- dianion. The character of electron density distribution in the C2B3 open face is analogous to the electron distribution in the cyclopentadienyl ligand. In nido-carborane, a substantial charge redistribution takes place compared to that observed in the closo analogs. The topological analysis of the electron density distribution function demonstrated that the cation-anion interactions are determined predominantly by Na...H-B contacts. The total energy of these contacts in the {[9-SMe2-7,8-C2B9H10]Na(thf)2}2 dimer estimated from X-ray diffraction data is 11.74 kcal mol-1

  18. Carborane Dopant Strengthens Pitch Char

    Science.gov (United States)

    Brown, D. Kyle

    1992-01-01

    Addition of small amount of soluble, organic boron compound to matrix precursor of carbon-fiber/carbon-matrix (carbon/carbon) composite increases strength and toughness of composite. Compound catalyzes graphitization of matrix, giving rise to greater degree of graphitization at lower processing temperature. Technique used to advantage in carbon/carbon materials requiring lower temperature processing, such as those with inhibited matrices or materials sensitive to changes in fiber properties.

  19. 含碳硼烷膦氧配体镍、铱化合物的合成与表征%Synthesis and Characterization of Ni(Ⅱ) and Ir(Ⅰ) Complex with o-Carborane [O,P] or [O,O] Ligand

    Institute of Scientific and Technical Information of China (English)

    蒋其柏; 季一飞; 沈旭杰; 燕红

    2013-01-01

    The reactions of o-carborane [P,P] ligand L1 with NiCl2(PPh3)2 and [IrCl(COD)]2 under an open atmosphere lead to two nido-carborane species 1 and 2 containing [O,P] or [O,O] ligands. All these complexes have been characterized by NMR, MS, IR and X-ray diffraction analyses. Complex 1 with solvent CHCl3 formed the normal C1…H interaction and novel CH…π interaction. Complex 2 is the first Ir(I) compound containing [O, P] o-carborane ligand. However, due to the difference of metal (Ni and Ir), the [P,P] ligand L1 was oxizided to novel [P,O] ligand and [O,O] ligand, respectively. CCDC: 927419, 1; 927420, 2.%碳硼烷双膦配体L1分别与三苯基膦氯化镍(NiCl2(PPh3)2)和1,5-环辛二烯氯化铱(IrCl(COD))在空气中反应生成含巢式碳硼烷膦氧配体的镍、铱化合物1和2.本文对此两个化合物进行了核磁、质谱、红外及单晶衍射等表征.化合物1中溶剂分子氯仿与主体结构存在着常见的Cl…H氢键作用和较少见的CH…π作用,化合物2是首例以膦氧配体形成的Ir(Ⅰ)配合物,同时由于金属的差别导致了碳硼烷双膦配体被氧化程度的不同形成了新颖的碳硼烷[P,O]和[O,O]配体.

  20. Carborane-containing metalloporphyrins for BNCT

    International Nuclear Information System (INIS)

    For BNCT of malignant brain tumors, it is crucial that there be relatively high boron concentrations in tumor compared with normal tissues within the neutron-irradiated treatment volume. Fairchild and Bond estimated that major advances in BNCT should be possible if ratios of 10B concentrations in tumor to those in normal tissue (e.g. brain and blood) were at least 5: 1. Given that the only current boron carrier being tested clinically in the U.S., p-boronophenyl-alanine[BPA], yields tumor blood and tumor brain ratios of about 3:1, the criteria for new boronated compounds should be to at least match these ratios and maintain tumor boron concentrations greater than 30 μg B/g. Although previously tested boronated porphyrins have not only matched but surpassed these ratios, it was at a cost of greater toxicity. Chemical and hematological assays of blood analytes; showed marked thrombocytopenia, a decrease to about one-tenth the normal concentration of platelets circulating in the blood, in addition to abnormalities in concentrations of circulating enzymes, that indicated liver toxicity. The physical appearance and behavior of the affected mice were different from those of mice injected with solvent only. Although thrombocytopenia and other toxic effects had disappeared after a few days, previously tested porphyrins would not be safe to infuse into patients for BNCT of potentially hemorrhagic malignant tumors in the brain such as glioblastoma multiforme and metastatic melanoma. We synthesized a different boronated porphyrin, tetracarboranylphenylporphyrin, [TCP] and inserted nickel, copper, or manganese into its coordination center. Biological studies of NiTCP in mice and of CuTCP in rats show that these compounds elicit little or no toxicity when given at potentially therapeutic doses

  1. Carborane-containing metalloporphyrins for BNCT

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Joel, D.D.; Nawrocky, M.M.; Micca, P.L. [and others

    1996-12-31

    For BNCT of malignant brain tumors, it is crucial that there be relatively high boron concentrations in tumor compared with normal tissues within the neutron-irradiated treatment volume. Fairchild and Bond estimated that major advances in BNCT should be possible if ratios of {sup 10}B concentrations in tumor to those in normal tissue (e.g. brain and blood) were at least 5: 1. Given that the only current boron carrier being tested clinically in the U.S., p-boronophenyl-alanine[BPA], yields tumor blood and tumor brain ratios of about 3:1, the criteria for new boronated compounds should be to at least match these ratios and maintain tumor boron concentrations greater than 30 {mu}g B/g. Although previously tested boronated porphyrins have not only matched but surpassed these ratios, it was at a cost of greater toxicity. Chemical and hematological assays of blood analytes; showed marked thrombocytopenia, a decrease to about one-tenth the normal concentration of platelets circulating in the blood, in addition to abnormalities in concentrations of circulating enzymes, that indicated liver toxicity. The physical appearance and behavior of the affected mice were different from those of mice injected with solvent only. Although thrombocytopenia and other toxic effects had disappeared after a few days, previously tested porphyrins would not be safe to infuse into patients for BNCT of potentially hemorrhagic malignant tumors in the brain such as glioblastoma multiforme and metastatic melanoma. We synthesized a different boronated porphyrin, tetracarboranylphenylporphyrin, [TCP] and inserted nickel, copper, or manganese into its coordination center. Biological studies of NiTCP in mice and of CuTCP in rats show that these compounds elicit little or no toxicity when given at potentially therapeutic doses.

  2. Medicinal Application of Carboranes Inhibition of HIV Protease

    Czech Academy of Sciences Publication Activity Database

    Řezáčová, Pavlína; Cígler, Petr; Matějíček, P.; Lepšík, Martin; Pokorná, Jana; Grüner, Bohumír; Konvalinka, Jan

    Boca Raton: CRC Press, 2012, s. 41-70. ISBN 978-1-4398-2662-1 R&D Projects: GA AV ČR IAAX00320901; GA MŠk LC512; GA MŠk LC523 Grant ostatní: 6th Framework(XE) QLRT2001-02360 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40320502 Keywords : metallacarboranes * resistance * inhibitor * HIV * AIDS Subject RIV: CE - Biochemistry

  3. Chiral separations of charged boranes and carboranes by CZE

    Czech Academy of Sciences Publication Activity Database

    Slavíček, Viktor; Vespalec, Radim

    Praha: Česká chemická společnost, 2001 - (Kašička, V.; Deyl, Z.), s. 51 ISBN 80-7080-437-8. [International Symposium Separations in the BioSciences /2./. Praha (CZ), 17.09.2002-20.09.2002] Institutional research plan: CEZ:AV0Z4031919 Keywords : deltahedral boranes * capillary zone electrophoresis * beta-cyclodextrin Subject RIV: CB - Analytical Chemistry, Separation

  4. Permethylated 12-Vertex p-Carborane Self-Assembled Monolayers

    Czech Academy of Sciences Publication Activity Database

    Scholz, F.; Nothofer, H. G.; Wessels, J. M.; Nelles, G.; Wrochem von, F.; Roy, S.; Chen, X.; Michl, Josef

    2011-01-01

    Roč. 115, č. 46 (2011), s. 22998-23007. ISSN 1932-7447 Grant ostatní: National Science Foundation(US) CHE-0848477 Institutional research plan: CEZ:AV0Z40550506 Keywords : p-carbone * monolayer * scanning tunneling microscopy * ultraviolet photoelectron spectroscopy * X-ray photoelectron Subject RIV: CC - Organic Chemistry Impact factor: 4.805, year: 2011

  5. On peculiarities of thermal and thermaloxidative destruction of 1.2-bis-(4-hydroxyphenyl) carborane and 1.2-bis-(4-carboxyphenyl) carborane polyarylates

    International Nuclear Information System (INIS)

    Difference in the behaviour of crystalic and amorphous samples of polyarylate 1.2-bis(4-oxyphenyl) carboron and 1.2-bis-(4-carboxyphenyl) carboron when heating is shown. It can be conditioned by the difference in the molecular mobility at 280-380 deg C. It was established that destruction of carboron containing polymers processes in the medium temperature region are leading to the formation of structures with B-O bounds

  6. Liposome and co-spray-dried PVP / o-carborane formulations for BNCT treatment of cancer

    OpenAIRE

    Olusanya, Temidayo; Stich, Theresia; Higgins, Samantha Caroline; Lloyd, Rhiannon Eleanor Iris; Pilkington, Geoffrey John; Fatouros, Dimitrios; Calabrese, Gianpiero; Smith, James Richard; Tsibouklis, John

    2015-01-01

    Purpose: Boron neutron capture therapy (BNCT) is a method for selectively destroying malignant (normally glioma) cells whilst sparing normal tissue. Irradiation of 10B (large neutron capture cross-section) with thermal neutrons effects the nuclear fission reaction: 10B + 1n → → 7Li+ + α + γ; where the penetration of α-particles and 7Li+ is only 8 and 5 µm, respectively, i.e., within a single cell thickness. Poor selectivity is the main reason why BNCT has not become a mainstream cancer therap...

  7. The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes.

    Science.gov (United States)

    Pitto-Barry, Anaïs; South, Amy; Rodger, Alison; Barry, Nicolas P E

    2016-01-28

    The functionalisation of the 16-electron complex [Os(η(6)-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)] (1) with a series of Lewis bases to give the 18-electron complexes of general formula [Os(η(6)-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)(L)] (L = pyridine (2), 4-dimethylaminopyridine (3), 4-cyanopyridine (4), 4-methoxypyridine (5), pyrazine (6), pyridazine (7), 4,4'-bipyridine (8) and triphenylphosphine (9)) is reported. All 18-electron complexes are in equilibrium in solution with the 16-electron precursor, and thermochromic properties are observed in some cases (2, 3, 5, 8, and 9). The binding constants and Gibbs free energies of the equilibria are determined using UV-visible titrations and their stabilities investigated. Synthetic routes for forcing the formation of the 18-electron species are proposed, and analytical methods to characterise the equilibria are described. PMID:26700880

  8. Carborane functionalized graphene oxide, a precursor for conductive self-assembled monolayers

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Bakardjieva, Snejana; Bakardjiev, Mario; Štíbr, Bohumil; Kormunda, M.

    2014-01-01

    Roč. 67, FEB (2014), s. 336-343. ISSN 0008-6223 R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : ATMOSPHERIC-PRESSURE PLASMA * X-RAY PHOTOELECTRON * HYBRID MATERIAL * BORON - CARBIDE * NANOSTRUCTURES Subject RIV: CA - Inorganic Chemistry Impact factor: 6.196, year: 2014

  9. Carborane-thiol-silver interactions. A comparative study of the molecular protection of silver surfaces

    Czech Academy of Sciences Publication Activity Database

    Baše, Tomáš; Bastl, Zdeněk; Havránek, Vladimír; Lang, Kamil; Bould, Jonathan; Londesborough, Michael Geoffrey Stephen; Macháček, Jan; Plešek, Jaromír

    2010-01-01

    Roč. 204, 16-17 (2010), s. 2639-2646. ISSN 0257-8972 R&D Projects: GA MŠk LC523; GA MŠk(CZ) LC06041; GA AV ČR IAA400320901; GA AV ČR(CZ) KAN400480701; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503; CEZ:AV0Z10480505 Keywords : silver * self assembly * corrosion * nanostructure Subject RIV: CA - Inorganic Chemistry Impact factor: 2.135, year: 2010

  10. Synthesis of carboranes containing an azulene framework and in vitro evaluation as boron carriers.

    Science.gov (United States)

    Nakamura, H; Sekido, M; Yamamoto, Y

    1997-08-29

    3-(o-Carboranylhydroxymethyl)-7-isopropylazulene sodium carboxylate (1) and 3-(o-carboranylmethyl)-7-isopropylazulene sodium sulfonate (2) were synthesized from the palladium-catalyzed addition reaction of 1-carboranyltributylstannane (4) to azulene aldehydes (3 and 9). Although the water solubility of 1 was of the order of 10(-6) M, that of 2 was of the order of 10(-3) M and was enough for clinical use. The cytotoxicity of 1 (IC50) toward B-16 melanoma cells was of the order of 10(-5) M, whereas that of 2 was of the order of 10(-4) M. This value was close to that of BPA (approximately 9 x 10(-3) M) which is utilized for clinical use. The boron uptake by B-16 cells was 0.17 microgram of B/10(6) cells for 1 and 0.25 microgram of B/10(6) cells for 2. It is clear that compound 2 accumulates in B-16 melanoma cells with a significantly high level although it is highly water soluble and its cytotoxicity is significantly low. PMID:9288164

  11. Unique stereocontrol in carborane chemistry: skeletal alkylcarbonation (SAC) versus exoskeletal alkylmethylation (EAM) reactions.

    Science.gov (United States)

    Bakardjiev, Mario; Holub, Josef; Macháček, Jan; Hnyk, Drahomír; Štíbr, Bohumil; Růžičková, Zdeňka; Růžička, Aleš

    2015-04-13

    Reactions between the arachno-6,9-C2B8H14 (1) dicarbaborane and acyl chlorides, RCOCl (2), are subject to stereocontrol that completely changes the nature of the reaction products. While most chlorides produce the 8-R-nido-7,8,9-C3B8H11 (3) tricarbollides (by skeletal alkylcarbonation=SAC), bulky RCOCls (2; where R=1-adamantyl, 2 a; 1-mesityl, 2 b; 9-anthranyl, 2 c; 1-naphthyl, 2 d) in 1,2-dichloroethane (DCE) in the presence of triethylamine at 40-60 °C gave a series of entirely different 1-R-2-CH3-closo-1,6-C2B8H8 (4) dicarbaboranes upon acidification with conc. H2SO4 (by exosleletal alkylmehylation=EAM). Both types of reactions seem to proceed via a common [8-R-nido-7,8,9-C3B8H10](-) (3(-)) anion which in the EAM case is unstable because of steric crowd and undergoes rearrangement via the isomeric [R-nido-7,8,10-C3B8H10](-) tricarbollide structures which, on protonation, undergo reductive extraction of one CH vertex to generate the 2-CH3 substituent in structure 4. PMID:25708127

  12. Anomalous behavior of the structural relaxation dispersion function of a carborane-containing siloxane

    Energy Technology Data Exchange (ETDEWEB)

    Pawlus, Sebastian; Paluch, Marian; Ziolo, Jerzy [Institute of Physics, University of Silesia, Uniwersytecka 4, Katowice 40-007 (Poland); Kolel-Veetil, Manoj K [Chemistry Division, Code 6127, Naval Research Laboratory, Washington, DC 20375-5342 (United States)

    2010-10-20

    Broadband dielectric spectroscopic investigations of a vinyl-terminated carboranylenesiloxane, VCS, were performed at ambient and elevated pressures. At a constant structural relaxation time, results show that the structural relaxation dispersion function of VCS narrows with both increasing pressure and temperature. This narrowing is substantial in the case of pressurization and, consequently, the breakdown of the temperature-pressure superposition rule is observed. The interpretation of this breakdown is presented.

  13. o-Carborane functionalized pentacenes: synthesis, molecular packing and ambipolar organic thin-film transistors.

    Science.gov (United States)

    Guo, Jixi; Liu, Danqing; Zhang, Jiahui; Zhang, Jiji; Miao, Qian; Xie, Zuowei

    2015-08-01

    New 6,13-bis[1'-(C≡C)-2'-R-1',2'-C2B10H10]pentacenes (R = H, Me, Et, n-Bu) are synthesized and fully characterized. The results show that the alkyl substituents on the second cage carbon have a significant impact on the molecular packing, and the incorporation of the o-carboranyl moiety into a π conjugated system can lower both LUMO and HOMO energy levels, converting a typical p-type semiconductor into an ambipolar one. PMID:26121634

  14. Transferrin-loaded nido-carborane liposomes. Synthesis and intracellular targeting to solid tumors for boron neutron capture therapy

    International Nuclear Information System (INIS)

    The boron ion cluster lipids, as a double-tailed boron lipid synthesized from heptadecanol, formed stable liposomes at 25% molar ratio toward DSPC with cholesterol. Transferrin was able to be introduced on the surface of boron liposomes (Tf-PEG-CL liposomes) by the coupling of transferrin to the PEG-CO2H moieties of PEG-CL liposomes. The biodistribution of Tf-PEG-CL liposomes showed that Tf-PEG-CL liposomes accumulated in tumor tissues and stayed there for a sufficiently long time to increase tumor:blood concentration ratio. A 10B concentration of 22 ppm in tumor tissues was achieved by the injection of Tf-PEG-CL liposome at 7.2 mg/kg body weight 10B in tumor-bearing mice. After neutron irradiation, the average survival rate of mice not treated with Tf-PEG-CL liposomes was 21 days, whereas that of the treated mice was 31 days. Longer survival rates were observed in the mice treated with Tf-PEG-CL liposomes; one of them even survived for 52 days after BNCT. (author)

  15. Synthesis and reaction of 16-electron CptRh halfsandwich complexes containing 1,2-dichalcogenolate carborane ligands

    Institute of Scientific and Technical Information of China (English)

    KONG Qingan; JIN Guoxin; CAI Shuyi; WENG Linhong

    2003-01-01

    The reactions of [CptRhCl((-Cl)]2 (1) (Cpt = tBu2C5H3) with Li2E2C2B10H10 (E = S, Se) lead to the green 16-electron dichalcogenolate complexes CptRh(E2C2B10H10) [E = S(2a), Se(2b)]. The 16-electron complexes 2a and 2b can take up two-electron donor ligands such as tert-butyl isonitrile and carbon monoxide to give the 18-electron dichalcogenolate derivatives Cpt(L)(E2C2B10H10) [L = tBuNC, E = S(3a), Se(3b); L = CO, E = S(4a), Se(4b)]. The molecular structures of complexes 2a and 3a were determined by X-ray crystal structure analysis. The molecular structure of 16- electron complex 2a shows the pseudoaromatic system in IrSe2C2 five numbered ring.

  16. Sandwich iridium complexes with the monoanionic carborane ligand [9-SMe2-7,8-C2B9H10]-

    International Nuclear Information System (INIS)

    The reaction of the [(η-9-SMe2-7,8-C2B9H10)IrBr2]2 complex with Tl[Tl(η-7,8-C2B9H11)] afforded the iridacarborane compound (η-9-SMe2-7,8-C2B9H10)Ir(η-7,8-C2B9H11). The cationic complex [Cp*Ir(η-9-SMe2-7,8-C2B9H10)]+PF6- (Cp* is pentamethylcyclopentadienyl) was synthesized by the reaction of [Cp*IrCl2]2 with Na[9-SMe2-7,8-C2B9H10]. The structures of (η-9-SMe2-7,8-C2B9H10)Ir(η-cod) (cod is 1,5-cyclooctadiene) and [Cp*Ir(η-9-SMe2-7,8-C2B9H10]PF6 were established by X-ray diffraction

  17. Cationic Closo-carboranes 2. Do computed 11B and 13C NMR chemical shifts support their experimental availability?

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Jayasree, E.G.

    2013-01-01

    Roč. 34, č. 8 (2013), s. 656-661. ISSN 0192-8651 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : boron clusters * weakly-coordinating cations * 11B NMR * dynamic electron correlation Subject RIV: CA - Inorganic Chemistry Impact factor: 3.601, year: 2013

  18. Silver and Copper Complexes with closo-Polyhedral Borane, Carborane and Metallacarborane Anions: Synthesis and X-ray Structure

    Directory of Open Access Journals (Sweden)

    Varvara V. Avdeeva

    2016-05-01

    Full Text Available Synthesis and structure of silver and copper salts and complexes with polyhedral boron hydride anions, including closo-decaborate [B10H10]2−, closo-dodecaborate [B12H12]2−, 1-carba-closo- decaborate [1-CB9H10]−, carba-closo-dodecaborate [CB11H12]−, and cobalt bis(dicarbollide [3,3′-Co(1,2-C2B9H112]− anions and their derivatives, are reviewed. The complexes demonstrate a wide variety of structural types, relating to both the metal coordination environment and coordination modes of boron hydride anions. The latter can range from strong coordination via the polyhedron triangular face including formation of 3c-2e MHB bonds in the case of the [B10H10]2− dianion, the structure of which contains two four-coordinated boron atoms, to very weak M…H interactions with the hydride atoms in the case of bulky [3,3′-Co(1,2-C2B9H112]− monoanion.

  19. QM/MM Calculations Reveal the Different Nature of the Interaction of Two Carborane-Based Sulfamide Inhibitors of Human Carbonic Anhydrase II

    Czech Academy of Sciences Publication Activity Database

    Pecina, Adam; Lepšík, Martin; Řezáč, Jan; Brynda, Jiří; Mader, Pavel; Řezáčová, Pavlína; Hobza, Pavel; Fanfrlík, Jindřich

    2013-01-01

    Roč. 117, č. 50 (2013), s. 16096-16104. ISSN 1520-6106 R&D Projects: GA ČR GBP208/12/G016 Grant ostatní: Operational Program Research and Development for Innovations(XE) CZ 1.05/2.1.00/03/0058 Institutional support: RVO:61388963 ; RVO:68378050 Keywords : neutron-capture therapy * dodecaborate cluster lipids * boron clusters Subject RIV: CF - Physical ; Theoretical Chemistry; EB - Genetics ; Molecular Biology (UMG-J) Impact factor: 3.377, year: 2013

  20. Molecular Rods Combining o-Carborane and Bicyclo[1.1.1]pentane Cages: An Insertion of the Triple Bond Located Next to a Highly Strained Cage

    Czech Academy of Sciences Publication Activity Database

    Kaleta, Jiří; Janoušek, Zbyněk; Nečas, M.; Mazal, C.

    2015-01-01

    Roč. 34, č. 5 (2015), s. 967-972. ISSN 0276-7333 Grant ostatní: GA MŠk(CZ) ED1.1.00/02.0068 Institutional support: RVO:61388963 Keywords : dehydrogenative alkyne-insertion * dicobalt octacarbonyl * polyborane reactions Subject RIV: CC - Organic Chemistry Impact factor: 4.126, year: 2014

  1. Thermochromic organometallic complexes: experimental and theoretical studies of 16- to 18-electron interconversions of adducts of arene Ru(II) carboranes with aromatic amine ligands.

    Science.gov (United States)

    Barry, Nicolas P E; Deeth, Robert J; Clarkson, Guy J; Prokes, Ivan; Sadler, Peter J

    2013-02-21

    A series of 18-electron complexes of general formula [Ru(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)(L)] (p-cym = para-cymene; L = 4-dimethylaminopyridine (2), nicotinamide (3), 3-ethynylpyridine (4), N-methylimidazole (5), 4-cyanopyridine (6), and pyridine (7)) were synthesised by reactions between the 16-electron precursor [Ru(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)] (1) and corresponding heterocyclic bases. X-ray crystal structures of complexes 2 and 5 were determined. In dichloromethane and chloroform solutions at ambient temperature, the 18-electron complexes 2-7 are in equilibrium with the 16-electron precursor 1. Each equilibrium is displaced towards the formation of the blue 16-electron or yellow 18-electron complex by increasing or decreasing the temperature of the solution, respectively, which results in controlled and reversible thermochromism. Binding constants (K) and Gibbs free energies (ΔG°) of the six equilibria have been determined by a combination of experiments (Job plots, UV-visible titrations, NMR studies) and also by computation (time-dependent density functional theory, TD-DFT). A linear free energy relationship for log K versus pK(a) for the pyridine and imidazole ligands was established. The predicted strong interactions of 1 with other aromatic amine ligands, such as amphetamine derivatives, were verified experimentally. This appears to be the first report of reversible 16/18-electron interconversions with associated thermochromic properties for a well-known family of complexes. PMID:23223796

  2. Carborane-based carbonic anhydrase inhibitors: insight into CAII/CAIX specificity from a high-resolution crystal structure, modeling, and quantum chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Mader, Pavel; Pecina, Adam; Cígler, Petr; Lepšík, Martin; Šícha, Václav; Hobza, Pavel; Grüner, Bohumír; Fanfrlík, Jindřich; Brynda, Jiří; Řezáčová, Pavlína

    2014-01-01

    Roč. 2014, Sept 18 (2014), 389869/1-389869/9. ISSN 2314-6133 R&D Projects: GA TA ČR(CZ) TE01020028; GA ČR GBP208/12/G016 Institutional support: RVO:61388980 ; RVO:68378050 ; RVO:61388963 Keywords : Drug design * Identification * Accuracy Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 1.579, year: 2014

  3. Expanding the structural chemistry of the weakly coordinating closo-carborane CB11H12 (-): its monoiodo derivatives with and without C (5v) symmetry

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Holub, Josef; Růžička, A.; Padělková, Z.; Bühl, M.

    2013-01-01

    Roč. 24, č. 3 (2013), s. 927-932. ISSN 1040-0400 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : Weakly-coordinating anions * X-Ray diffraction * B-11 Chemical shifts * Spin-orbit coupling * Acidity Subject RIV: CA - Inorganic Chemistry Impact factor: 1.900, year: 2013

  4. A photoelectron spectroscopic and computational study of the o-dicarbadodecaborane parent anion

    Science.gov (United States)

    Zhang, Xinxing; Bowen, Kit

    2016-06-01

    We report a combined photoelectron spectroscopic and computational study of the o-dicarbadodecaborane (o-carborane) parent anion, (C2B10H12)-. Previous studies that focused on the electrophilic nature of o-carborane led to tantalizing yet mixed results. In our study, we confirmed that o-carborane does in fact form a parent anion and that it has considerable stability. This anion is an isomer ("Anion iso 2") where unlike in neutral o-carborane, the two carbon atoms are not bound.

  5. A photoelectron spectroscopic and computational study of the o-dicarbadodecaborane parent anion.

    Science.gov (United States)

    Zhang, Xinxing; Bowen, Kit

    2016-06-14

    We report a combined photoelectron spectroscopic and computational study of the o-dicarbadodecaborane (o-carborane) parent anion, (C2B10H12)(-). Previous studies that focused on the electrophilic nature of o-carborane led to tantalizing yet mixed results. In our study, we confirmed that o-carborane does in fact form a parent anion and that it has considerable stability. This anion is an isomer ("Anion iso 2") where unlike in neutral o-carborane, the two carbon atoms are not bound. PMID:27306011

  6. Update 1 of: Chemistry of the carba-closo-dodecaborate(-) anion, CB11H12(-)

    Czech Academy of Sciences Publication Activity Database

    Douvris, Christos; Michl, Josef

    2013-01-01

    Roč. 113, č. 10 (2013), PR179-PR233. ISSN 0009-2665 Grant ostatní: NSF(US) CHE-0848477 Institutional support: RVO:61388963 Keywords : carboranes * carborane anions * electrochemistry * spectroscopy * synthesis Subject RIV: CC - Organic Chemistry Impact factor: 45.661, year: 2013

  7. Reaction Development on π- and σ-Conjugated Bonds and Creation of Innovative Functions.

    Science.gov (United States)

    Takita, Ryo

    2016-01-01

    Monocarba-closo-dodecaborate (1; [closo-CB11H12](-), or C1-carborane anion) is a symmetrical, stable anionic cluster, which possesses low nucleophilicity/basicity and exhibits three-dimensional aromaticity. In contrast to the rich applications of C2-carborane molecules (C2B10H12), the chemistry of the C1-carborane anion as a platform for functional molecules has not been thoroughly studied thus far due to the lack of its efficient functionalization. In particular, no efficient general methods are available for the introduction of aryl and sp(2)/sp-carbon groups at the carbon vertex of the C1-carborane anion. The unique electronic structure and potential applications of the C1-carborane anion prompted us to investigate methods to functionalize it. We developed a general, efficient C-C cross-coupling reaction of 1 under palladium catalysis which yields a variety of 1-C-functionalized C1-carborane derivatives. The use of copper(I) or lithium species as a transmetalating partner facilitated the cross-coupling process of the sterically hindered C1-carborane anion. The potential application of 1-C-arylated C1-carborane anion derivatives thus obtained were explored, some of which showed potential as pharmacophores and ionic liquid crystal behavior. Furthermore, conjugation between σ- and π-aromatic moieties in 1-C-arylated monocarba-closo-dodecaborate anion derivatives was identified by means of kinetic experimental studies combined with theoretical calculations. PMID:27252066

  8. Boron loaded scintillator

    Energy Technology Data Exchange (ETDEWEB)

    Bell, Zane William [Oak Ridge, TN; Brown, Gilbert Morris [Knoxville, TN; Maya, Leon [Knoxville, TN; Sloop, Jr., Frederick Victor (Oak Ridge, TN); Sloop, Jr., Frederick Victor [Oak Ridge, TN

    2009-10-20

    A scintillating composition for detecting neutrons and other radiation comprises a phenyl containing silicone rubber with carborane units and at least one phosphor molecule. The carbonate units can either be a carborane molecule dispersed in the rubber with the aid of a compatibilization agent or can be covalently bound to the silicone.

  9. Synthesis, Characterization and High Temperature Resistance of Diglycidyl Ether of Carborane Bisphenol%碳硼烷双酚二缩水甘油醚的合成与表征及耐高温性能研究

    Institute of Scientific and Technical Information of China (English)

    齐士成; 汪尧双; 韩果; 杨震; 张孝阿; 江盛玲; 吕亚非

    2015-01-01

    以o-(3)和m-碳硼烷双酚(4)为原料,经两步法合成了o-(1)和m-碳硼烷双酚二缩水甘油醚(2),FTIR、1H-NMR、GPC和环氧值测试都表明得到了预期结构的碳硼烷环氧树脂.固化反应动力学研究结果显示,1/DDS和2/DDS体系的反应活化能(Ea)分别为79.0和67.1 kJ·mol-1,比E-51/DDS略高,说明碳硼烷结构的存在降低了环氧树脂的反应活性.以Ea结果为依据,确定了1(2)/DDS体系的固化工艺为180℃/2h+200℃/2h.热分析结果表明,以DDS为固化剂时,1和2的Tg分别为175.8和167.6℃,高于TDE-85的154.1℃.TGA结果表明,2/DDS固化物在空气气氛下700℃的残炭率高达78.7%,说明碳硼烷结构的存在极大提高了环氧树脂高温稳定性.碳硼烷环氧树脂空气气氛中的高温残炭率比氮气中高,原因是碳硼烷结构中的B-H键与空气中的氧气反应生成B—O—B结构,因而提高了残炭率,并在一定程度上延缓了体系的失重.

  10. Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC-CB11X11(-) (X = H, F, CH3) as Ligands on Pt(II) and Pd(II).

    Science.gov (United States)

    Šembera, Filip; Plutnar, Jan; Higelin, Alexander; Janoušek, Zbyněk; Císařová, Ivana; Michl, Josef

    2016-04-18

    The anionic nitriles 1-R-12-NC-CB11H10(-) (R = H, CH3, I, COOH), 12-NC-1-H-CB11Me10(-), and 12-NC-1-H-CB11F10(-) were prepared, and three of them were examined for complex formation with (Et3P)2Pt(II) and (Et3P)2Pd(II). Several stable internally charge-compensated zwitterionic complexes were obtained and characterized. RI-BP86/SV(P) calculations suggest that their dipole moments exceed 20 D. An attempt to measure the dipole moments in solution failed due to insufficient solubility in solvents of low polarity. PMID:27018918

  11. Synthesis and cytotoxicity of boronated fatty esters for BNCT of cervix cancer

    International Nuclear Information System (INIS)

    Esterification reactions of o-carboranic acid with six fatty alcohols, palmitoleyl, stearyl, oleyl, elaidyl, linoleyl and linoelaidyl alcohols, proceeded smoothly under nitrogen atmosphere with dimethylamino pyrimidine as a catalyst. The reaction gave the corresponding esters in moderate yields. Most of the synthetic esters are stable at room temperature except the linoleyl carboranate and linoelaidyl carboranate which decomposed within two weeks. The in vitro studies on Hela cells showed relatively low cytotoxic. The IC50 of boronated esters were in range of 36-83 micrograms/cm3. (author)

  12. First boronization in KSTAR

    Energy Technology Data Exchange (ETDEWEB)

    Hong, S.H., E-mail: sukhhong@nfri.re.kr [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Lee, K.S.; Kim, K.M.; Kim, H.T.; Kim, G.P. [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Sun, J.H.; Woo, H.J. [Department of Electrical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of); Park, J.M.; Kim, W.C.; Kim, H.K.; Park, K.R.; Yang, H.L.; Na, H.K. [National Fusion Research Institute, 113 Gwahangno, Yusung-Gu, Daejeon 305-333 (Korea, Republic of); Chung, K.S. [Department of Electrical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Center for Edge Plasma Science (cEps), Hanyang University, Seoul 133-791 (Korea, Republic of)

    2010-11-15

    First boronization in KSTAR is reported. KSTAR boronization system is based on a carborane (C{sub 2}B{sub 10}H{sub 12}) injection system. The design, construction, and test of the system are accomplished and it is tested by using a small vacuum vessel before it is mounted to a KSTAR port. After the boronization in KSTAR, impurity levels are significantly reduced by factor of 3 (oxygen) and by 10 (carbon). Characteristics of a-C/B:H thin films deposited by carborane vapor are investigated. Re-condensation of carborane vapor during the test phase has been reported.

  13. Cross-metathesis of allylcarboranes with O-allylcyclodextrins

    Czech Academy of Sciences Publication Activity Database

    Šnajdr, I.; Janoušek, Zbyněk; Jindřich, J.; Kotora, M.

    2010-01-01

    Roč. 6, - (2010), s. 1099-1105. ISSN 1860-5397 Institutional research plan: CEZ:AV0Z40320502 Keywords : carborane * catalysis * cross-metathesis Subject RIV: CC - Organic Chemistry Impact factor: 1.515, year: 2010

  14. Modulární laboratorní fluorová linka v ÚOCHB AV ČR

    Czech Academy of Sciences Publication Activity Database

    Valášek, Michal; Šembera, Filip; Janoušek, Zbyněk; Michl, Josef

    2014-01-01

    Roč. 108, č. 4 (2014), s. 394-397. ISSN 0009-2770 Institutional support: RVO:61388963 Keywords : carboranes * fluorine * hydrogen fluoride Subject RIV: CC - Organic Chemistry Impact factor: 0.272, year: 2014

  15. Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes

    Czech Academy of Sciences Publication Activity Database

    Kaleta, Jiří; Akdag, Akin; Crespo, R.; Piqueras, M. C.; Michl, Josef

    2013-01-01

    Roč. 78, č. 9 (2013), s. 1174-1183. ISSN 2192-6506 Institutional support: RVO:61388963 Keywords : alkylation * boranes * carboranes * electrophilic substitution * hydrogen scrambling Subject RIV: CC - Organic Chemistry Impact factor: 3.242, year: 2013

  16. 15th International Conference on Boron Chemistry (IMEBORON XV)

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Štíbr, Bohumil

    2015-01-01

    Roč. 87, č. 2 (2015), s. 121. ISSN 0033-4545 Institutional support: RVO:61388980 Keywords : boranes * boron * boron materials * carboranes * IMEBORON XV * medicinal chemistry Subject RIV: CA - Inorganic Chemistry

  17. Boron ion beam production with the supernanogan ECR ion source for the CERN BIO-LEIR facility

    CERN Document Server

    Stafford-Haworth, J; Scrivens, R; Toivanen, V; Röhrich, J

    2014-01-01

    To deliver B3+ ions for medical research the compounds decaborane and m-carborane were tested using the metal ions from volatile compounds (MIVOC) method with the Supernanogan 14.5 GHz ECR ion source. Using decaborane the source delivered less than 10 A intensity of B3+ and after operation large deposits of material were found inside the source. Using m-carborane 50 A of B3+ were delivered without support gas. For m-carborane, helium and oxygen support gasses were also tested, and the effects of different source tuning parameters are discussed. The average consumption of m-carborane was 0:1 mg/Ah over all operation.

  18. Synthesis of conjugates of polyhedral boron compounds with tumor-seeking molecules for neutron capture therapy

    Energy Technology Data Exchange (ETDEWEB)

    Bregadze, V., E-mail: bre@ineos.ac.ru [A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, Moscow 119991 (Russian Federation); Semioshkin, A.; Sivaev, I. [A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, Moscow 119991 (Russian Federation)

    2011-12-15

    Recent achievements in design and synthesis of boronated acids, amino acids, glycerols as well as conjugates of polyhedral boron hydrides (ortho-carborane, closo-dodecaborate and cobalt bis(dicarbollide)) with natural porphyrins, carbohydrates and nucleosides are described.

  19. Synthesis of 3,4-{omicron}-Carboranylenepiperidine derivatives as potential BNCT agents

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chai Ho [Wonkwang University, Iksan (Korea, Republic of); Kang, Sang Ook [Korea University, Seoul (Korea, Republic of); Chun, Ki Jung; Park, Kyung Bae [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    Acovienient method for piperidines containing {omicron}-carborane moiety is described. 5a, 5b, 5d, and 5e were found accumulate in B-16 melanoma cells with a significantly high level, although with low cytotoxicity.

  20. Synthesis, crystal and molecular structure of 1-methyl-2-(-1-germa-tranil)-1,2-dicarba-closo-dodeca-borane, C9H25B10GeNO3

    International Nuclear Information System (INIS)

    By successive reactions, consisting in metallation of 1-methylcarborane by ethylmagnesiumbromide, interaction of the product with germanium tetrachloride and then with tris (trimethylsililoxyethyl) amine with 37% yield, a compound containing fragments of carborane and germatrane with Ge-C (carborane) bond has been synthesized for the first time. The structure of the compound prepared is studied by the methods of 1H and 11B NMR, as well as by X-ray diffraction analysis

  1. Synthesis, Spectra Characterization and Crystal Structure of Three Nickle(Ⅱ) Complexes Containing Nido-carborane Disphosphine Ligand%三个巢式磷碳硼烷镍配合物的合成、光谱表征和晶体结构

    Institute of Scientific and Technical Information of China (English)

    杨立国; 张道鹏; 李大成; 窦建民

    2013-01-01

    合成了3个巢式磷碳硼烷镍配合物[NiCl(Py){7,8-(PPh2)2-7,8-C2B9H10}]· CH2Cl2(1)、[Ni{7,8-(PPh2)2-7,8-C2B9H10}2](2)、[Ni{7,8-(OPPh2)-7,8-C2B9H10}{7,8-(PPh2)-7,8-C2B9H10}](3),并通过元素分析、红外光谱、核磁共振谱以及单晶衍射等手段对其进行了表征.单晶结构分析表明,镍离子的配位环境在这3个配合物中都是稍微扭曲的平面方形,其中2个配位位置由磷碳硼烷配体的两个磷原子占据,另外2个配位位置分别由氯离子、吡啶氮原子或者氧化的磷碳硼烷配体的氧原子占据.借助于分子间的C-H…Cl氢键或者C-H.H-B双氢键作用,3个配合物都可以形成一维超分子结构.

  2. nido-C2B9H112-碳硼烷异构体结构和稳定性的密度泛函研究%Density functional theory study on the structures and stabilities of nido-C2B9H112-carborane isomers

    Institute of Scientific and Technical Information of China (English)

    魏洪源; 孙志忠; 李传友; 罗顺忠

    2014-01-01

    采用密度泛函方法对11顶点巢式碳硼烷C2B9H112-异构体进行了几何结构优化,分析了稳定性、电荷分布及分子轨道.结果表明,9个异构体都有对应的稳定构型,保持了巢式骨架结构.C取代开口五元环上B的异构体更稳定,且随取代数目增加和C原子间距增加而增加,C-C键和C-B键作用增强.C取代内层B使异构体稳定性降低,C C键和C-B键长随之增长.负电荷主要集中在C原子上,开口五元环上的C原子上负电荷要比内层C原子更多,成为亲核取代反应中心.异构体分子前线轨道具有和η5-C5H5-相似的π键性质,ΔELUMO-HOMO反映的化学稳定性与结构能量稳定性趋势一致.

  3. Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solidstate investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11

    Czech Academy of Sciences Publication Activity Database

    Baše, Tomáš; Macháček, Jan; Hájková, Zuzana; Langecker, Jens; Kennedy, John David; Carr, MJ.

    2015-01-01

    Roč. 798, č. 1 (2015), s. 132-140. ISSN 0022-328X R&D Projects: GA ČR GAP205/10/0348 Institutional support: RVO:61388980 Keywords : Carboranethiol * Isomerisation * Thermal Stability * Closo-dicarbadodecaboranes * Closo-dicarbadodecaborane thiol Subject RIV: CA - Inorganic Chemistry Impact factor: 2.173, year: 2014

  4. Molecular ion sources for low energy semiconductor ion implantation (invited)

    Science.gov (United States)

    Hershcovitch, A.; Gushenets, V. I.; Seleznev, D. N.; Bugaev, A. S.; Dugin, S.; Oks, E. M.; Kulevoy, T. V.; Alexeyenko, O.; Kozlov, A.; Kropachev, G. N.; Kuibeda, R. P.; Minaev, S.; Vizir, A.; Yushkov, G. Yu.

    2016-02-01

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C4H12B10O4) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH3 = P4 + 6H2; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P4+ ion beams were extracted. Results from devices and some additional concepts are described.

  5. Chemistry and Application of Dicarbadodecaborane and Its Derivatives%碳十硼烷及其衍生物的反应性及应用

    Institute of Scientific and Technical Information of China (English)

    赵娟; 黄鹏程; 陈功; 詹茂盛

    2012-01-01

    碳十硼烷(C2B10H12)是由2个C原子和10个B原子组成的二十面体笼状结构大分子,有邻位、间位和对位三种异构体。碳十硼烷庞大的体积以及类芳香族三维刚性结构使它具有优异的高温稳定性和化学稳定性,良好的溶解性使其具有广泛而灵活的应用。本文总结了近年来碳十硼烷和碳十硼烷衍生物在C原子、B原子上的化学反应性以及在环加成和金属络合方面的研究。另外,由于碳十硼烷衍生物特殊的立体结构,优异的耐高温性、热氧化性及高硼含量,本文综述了碳十硼烷衍生物近年来在功能材料、催化剂及生物医药等多个领域的应用进展。%Dicarba-closo-dodecaborane (carborane, C2B10HI2) containing two carbon atoms and ten boron atoms adopts nearly icosahedral geometry in which the carbon and boron atoms are hexacoordinate. The compound exists as ortho-, meta-and para-isomers. Due to the strong electron-acceptor properties of the cluster, massive bulk and three-dimensional rigidity, carborane and its derivatives possess remarkable thermal and chemical stability. Besides, the ready solubility makes the compound and its derivatives widely applied. There are two common methods for synthesis of carborane and carborane derivatives, including the "alkyne insertion" methodology and the method based on the substitution reaction with carboranyl lithium. In this paper, the chemical reactions and functionalization of carborane and its derivatives are summarized, especially the substitution reactions on carbon atoms and boron atoms, the cycloaddition reaction and metal-carborane complexation. Futhermore, due to the excellent heat stability and high electronic delocalization, the carborane derivatives can be utilized as functional materials. Also, carborane derivatives can be applied in boron neutron capture therapy (BNCT) for the high boron content of carborane. Meanwhile, the metal-carborane complexes

  6. Molecular ion sources for low energy semiconductor ion implantation (invited)

    International Nuclear Information System (INIS)

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C4H12B10O4) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH3 = P4 + 6H2; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P4+ ion beams were extracted. Results from devices and some additional concepts are described

  7. Molecular ion sources for low energy semiconductor ion implantation (invited).

    Science.gov (United States)

    Hershcovitch, A; Gushenets, V I; Seleznev, D N; Bugaev, A S; Dugin, S; Oks, E M; Kulevoy, T V; Alexeyenko, O; Kozlov, A; Kropachev, G N; Kuibeda, R P; Minaev, S; Vizir, A; Yushkov, G Yu

    2016-02-01

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C4H12B10O4) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH3 = P4 + 6H2; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P4(+) ion beams were extracted. Results from devices and some additional concepts are described. PMID:26932065

  8. Crystal structure of 1-butyl-2,3-dimethylimidazolium dicarba-7,8-nido-undecaborate

    Directory of Open Access Journals (Sweden)

    M. J. Klemes

    2015-03-01

    Full Text Available In the title molecular salt, C9H17N2+·C2H12B9−, the carborane cage has a bridging B—H—B bond on the open B3C2 face. The butyl side chain of the cation adopts an extended conformation [C—C—C—C = 179.6 (1°]. In the crystal, the imidazolium ring is almost coplanar with the open face of the carborane anion. The cations stack in the [010] direction and the dihedral angle between the imidazolium rings of adjacent cations is 68.45 (6°. The butyl chains extend into the space between carborane anions.

  9. Synthesis of small-scale boron-rich nano-size particles

    Energy Technology Data Exchange (ETDEWEB)

    Slutsky, Vladislav G.; Tsyganov, Sergei A.; Severin, Eugeny S.; Polenov, Leonid A. [Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin Street 4, 199991 Moscow (Russian Federation)

    2005-09-01

    The synthesis times required to produce high energy density compounds (C{sub 2}B{sub 4}H{sub 2}){sub n} and (C{sub 2}B{sub 10}H{sub 4}){sub n} by gas phase pyrolysis of the carboranes C{sub 2}B{sub 4}H{sub 6} and C{sub 2}B{sub 10}H{sub 12}, respectively, have been measured at 1150-2000 K and carborane pressures of (0.3-3.0).10{sup -3} MPa. Kinetic model simulations of the synthesis have been performed. The temperatures, carborane pressures, and synthesis times required to produce small-scale (C{sub 2}B{sub 4}H{sub 2}){sub n} and (C{sub 2}B{sub 10}H{sub 4}){sub n} particles of 10 to 30 nm diameter are determined. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

  10. Reaction of lithiumcarboranes with 1,2,4-triazine-4-oxides: the SNH reactions and cycle transformations

    International Nuclear Information System (INIS)

    The possibility of applying the reactions of the hydrogen nucleophilic substitution in the 1,2,4-triazine-4-oxides series for the synthesis of the heteroaryl carboranes is studied. It is established that the reaction of the 1-lithium-1,2- or 1,7-dicarbo-closo-dodecaborane with 1,2,4-triazine-4-oxides may proceed by two competing directions. Introduction of the acceptor 1,2,4-triazine cycle into the carborane skeleton may significantly facilitate the the deboration reaction process with formation of the 1-(1,2,4-triazine-5-yl)-1,2-1,7-dicarbo-nido-undecaboranes

  11. Carboranylporphyrins and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Renner, Mark W

    2012-10-16

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity carborane-containing porphyrin compounds with halide, amine, or nitro groups and methods for their use particularly in boron neutron capture therapy (BNCT), X-ray radiation therapy (XRT), and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these carborane-containing porphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  12. Carbonylporphyrins and uses thereof

    Science.gov (United States)

    Miura, Michiko; Renner, Mark W

    2014-03-18

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity carborane-containing porphyrin compounds with halide, amine, or nitro groups and methods for their use particularly in boron neutron capture therapy (BNCT), X-ray radiation therapy (XRT), and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these carborane-containing porphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  13. Carboranylporphyrins and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Haitao; Miura, Michiko

    2006-01-24

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity carborane-containing 5, 10, 15, 20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head, neck, and surrounding tissue. The invention is also directed to using these carborane-containing tetraphenyl porphyrin compounds to methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  14. Carboranylporphyrins and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Haitao; Miura, Michiko

    2006-02-07

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity carborane-containing 5, 10, 15, 20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these carborane-containing tetraphenyl porphyrin compounds to methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  15. Synthesis of the First Example of the 12-Vertex-closo/12-Vertex-nido Biscarborane Cluster by a Metal-Free B-H Activation at a Phosphorus(III) Center.

    Science.gov (United States)

    Wong, Yuen Onn; Smith, Mark D; Peryshkov, Dmitry V

    2016-05-10

    An unusual 12-vertex-closo-C2 B10 /12-vertex-nido-C2 B10 biscarborane cluster was synthesized through an unprecedented regioselective metal-free B-H activation by a sterically hindered P(III) center under mild conditions accompanied by cage-opening rearrangement. A combination of the electron-accepting properties of a carborane cage and steric enforcement of close interatomic contacts represent a new synthetic strategy for the activation of strong B-H bonds in carboranes. PMID:26990216

  16. Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Wu, Haitao

    2013-05-21

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  17. New multigram-scale preparation of 1,10-dicarba-closo-decabora

    Czech Academy of Sciences Publication Activity Database

    Holub, Josef; Jelínek, Tomáš; Janoušek, Zbyněk

    2002-01-01

    Roč. 67, č. 7 (2002), s. 949-952. ISSN 0010-0765 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes * ten-vertex Subject RIV: CA - Inorganic Chemistry Impact factor: 0.848, year: 2002

  18. Derivatization chemistry of the double-decker dicobalt sandwich ion targeted to design biologically active substances

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Švec, Petr; Hájková, Zuzana; Císařová, I.; Pokorná, Jana; Konvalinka, Jan

    2012-01-01

    Roč. 84, č. 11 (2012), s. 2243-2262. ISSN 0033-4545 R&D Projects: GA AV ČR IAAX00320901 Institutional support: RVO:61388980 ; RVO:61388963 Keywords : AIDS treatment * boranes * canastide ion * carboranes * dicarbollides * HIV -protease Subject RIV: CA - Inorganic Chemistry Impact factor: 3.386, year: 2012

  19. Electrochemistry of parent and exo-skeletally substituted icosahedral monocarba and dicarbaboranes and their derivatives at the graphite carbon electrode in aqueous phosphate buffers

    Czech Academy of Sciences Publication Activity Database

    Fojt, Lukáš; Fojta, Miroslav; Grüner, Bohumír; Vespalec, Radim

    2014-01-01

    Roč. 730, SEP15 (2014), s. 16-19. ISSN 1572-6657 R&D Projects: GA ČR(CZ) GBP206/12/G151 Institutional support: RVO:68081707 ; RVO:61388980 Keywords : Boranes * Carboranes * Glassy carbon electrode Subject RIV: BO - Biophysics; CA - Inorganic Chemistry (UACH-T) Impact factor: 2.729, year: 2014

  20. Chemistry of cobalt bis(1,2-dicarbollide) ion; the synthesis of carbon substituted alkylamino derivatives from hydroxyalkyl derivatives via methylsulfonyl or p-toluenesulfonyl esters

    Czech Academy of Sciences Publication Activity Database

    Nekvinda, Jan; Švehla, Jaroslav; Císařová, I.; Grüner, Bohumír

    2015-01-01

    Roč. 798, č. 1 (2015), s. 112-120. ISSN 0022-328X R&D Projects: GA ČR GA15-05677S Institutional support: RVO:61388980 Keywords : Boranes * Carboranes * Metallacarboranes * Dicarbollide * Building blocks Subject RIV: CA - Inorganic Chemistry Impact factor: 2.173, year: 2014

  1. Studies on Am(III) separation from simulated high-level waste using cobalt bis(dicarbollide) (1(-)) ion derivative covalently bound to N,N'-di-n-octyl diglycol diamide as extractant and DTPA as stripping agent

    Czech Academy of Sciences Publication Activity Database

    Bubeníková, M.; Selucký, P.; Rais, J.; Grüner, Bohumír; Švec, Petr

    2012-01-01

    Roč. 293, č. 1 (2012), s. 403-408. ISSN 0236-5731 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : Solvent extraction * actinides * high- level liquid waste * dicarbollide derivatives * carboranes * TODGA * DTPA Subject RIV: CA - Inorganic Chemistry Impact factor: 1.467, year: 2012

  2. New carbon-carbon linked amphiphilic carboranyl-porphyrins as boron neutron capture agents

    International Nuclear Information System (INIS)

    Novel amphiphilic carboranyl-porphyrins have been synthesized for Boron Neutron Capture Therapy (BNCT). These compounds have carbon-carbon bonds between the carborane residues and the porphyrin meso-phenyl groups, and contain 28-31% boron by weight . (author)

  3. Synthesis, Molecular Structure, and Electrochemistry of 1-Ferrocenyl-1,2-dicarba-closo-dodecaboranes

    Czech Academy of Sciences Publication Activity Database

    Korotvička, A.; Šnajdr, I.; Štěpnička, P.; Císařová, I.; Janoušek, Zbyněk; Kotora, M.

    -, č. 15 (2013), s. 2789-2798. ISSN 1434-1948 Grant ostatní: GA ČR(CZ) GAP207/11/0338; GAČR(CZ) GAP207/11/0705 Institutional support: RVO:61388963 Keywords : carboranes * metallocenes * structure elucidation * electrochemistry * addition Subject RIV: CA - Inorganic Chemistry Impact factor: 2.965, year: 2013

  4. Halogen protected cobalt bis(dicarbollide) ions with covalently bonded CMPO functions as anionic extractants for trivalent lanthanide/actinide partitioning

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Švec, Petr; Selucký, P.; Bubeníková, M.

    2012-01-01

    Roč. 38, č. 1 (2012), s. 103-112. ISSN 0277-5387 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * CMPR * liquid-liquid extraction * lanthanides * actinides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.813, year: 2012

  5. Cobalt bis(dicarbollide) ions functionalized by CMPO-like groups attached to boron by short bonds; efficient extraction agents for separation of trivalent f-block elements from highly acidic nuclear waste

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Kvíčalová, Magdalena; Plešek, Jaromír; Šícha, Václav; Císařová, I.; Lučaníková, M.; Selucký, P.

    2009-01-01

    Roč. 694, č. 11 (2009), s. 1678-1689. ISSN 0022-328X R&D Projects: GA MŠk LC523; GA AV ČR IAA400310613 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallacarbaboranes * liquid-liquid extraction Subject RIV: CA - Inorganic Chemistry Impact factor: 2.347, year: 2009

  6. The Zwitterion [8,8′-μ-CH2O(CH3)-(1,2-C2B9H10)2-3,3′-Co]0 as a Versatile Building Block To Introduce Cobalt Bis(Dicarbollide) Ion into Organic Molecules

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Grüner, Bohumír; Šícha, Václav; Böhmer, V.; Císařová, I.

    2012-01-01

    Roč. 31, č. 5 (2012), s. 1703-1715. ISSN 0276-7333 R&D Projects: GA MŠk LC523; GA AV ČR IAAX00320901 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * carboranes * dicarbollides * X-ray diffraction * NMR Subject RIV: CA - Inorganic Chemistry Impact factor: 4.145, year: 2012

  7. Anionic tert-butyl-calix[4]arenes substituted at the narrow and wide rim by cobalt bis(dicarbollide)(1-) ions and CMPO-groups. Effect of stereochemistry and ratios of the functional groups on the platform on the extraction efficiency for Ln(III)/An(III)

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Böhmer, V.; Dordea, C.; Selucký, P.; Bubeníková, M.

    2013-01-01

    Roč. 747, december (2013), s. 155-166. ISSN 0022-328X R&D Projects: GA ČR GA104/09/0668 Institutional support: RVO:61388980 Keywords : Actinides * Calixarenes * Carboranes * Lanthanides * Liquid-liquid extraction Subject RIV: CA - Inorganic Chemistry Impact factor: 2.302, year: 2013

  8. Anionic Oligomerization of Li-2[B12H12] and Li[CB11H12]: An Experimental and Computational Study

    Czech Academy of Sciences Publication Activity Database

    Dávalos, J. Z.; Gonzalez, J.; Guerrero, A.; Hnyk, Drahomír; Holub, Josef; Oliva, J. M.

    2013-01-01

    Roč. 117, č. 3 (2013), s. 1495-1501. ISSN 1932-7447 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : mass-spectrometry * carboranes * chemistry Subject RIV: CA - Inorganic Chemistry Impact factor: 4.835, year: 2013

  9. An unexpected rearrangement of carbon vertexes in the tricarbollide series. Asymmetrical 7-aryl-nido-7,8,9-C3B8H11 derivatives

    Czech Academy of Sciences Publication Activity Database

    Bakardjiev, Mario; Holub, Josef; Hnyk, Drahomír; Štíbr, Bohumil; Růžičková, Z.; Růžička, A.

    2016-01-01

    Roč. 805, MAR (2016), s. 117-121. ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : Boron hydrides * Carboranes * NMR spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 2.173, year: 2014

  10. Supramolecular variations based on cobalt bis(dicarbollide)(1-)ion

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Mikulášek, Libor; Báča, Jiří; Císařová, I.; Bőhmer, V.

    Průhonice, 2004, O18. [European Meeting on Boron Chemistry /3./. Průhonice (CZ), 12.09.2004-16.09.2004] R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * carboranes Subject RIV: CA - Inorganic Chemistry

  11. Simple Synthesis, Halogenation, and Rearrangement of closo-1,6-C2B8H10

    Czech Academy of Sciences Publication Activity Database

    Bakardjiev, Mario; Štíbr, Bohumil; Holub, Josef; Padělková, Z.; Růžička, A.

    2015-01-01

    Roč. 34, č. 2 (2015), s. 450-454. ISSN 0276-7333 R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : MAGNETIC-RESONANCE-SPECTROSCOPY * ORGANOELEMENTAL DERIVATIVES * CLOSO-BORANES * CARBORANES * 5,6-DICARBA-NIDO-DECABORANE(12) Subject RIV: CA - Inorganic Chemistry Impact factor: 4.126, year: 2014

  12. Transmission of Electronic Substituent Effects across the 1,12-Dicarba-doso-dodecaborane Cage: A Computational Study Based on Structural Variation, Atomic Charges, and C-13 NMR Chemical Shifts

    Czech Academy of Sciences Publication Activity Database

    Campanelli, A.R.; Domenicano, A.; Hnyk, Drahomír

    2015-01-01

    Roč. 119, č. 1 (2015), s. 205-214. ISSN 1089-5639 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : MONOSUBSTITUTED BENZENE RINGS * 4-SUBSTITUTED BIPHENYLS * 3-DIMENSIONAL AROMATICITY * CARBORANES * DERIVATIVES Subject RIV: CA - Inorganic Chemistry Impact factor: 2.693, year: 2014

  13. A computational analysis of the apparent nido vs. hypho conflict: Are we dealing with six- or eight-vertex open-face diheteroboranes?

    Czech Academy of Sciences Publication Activity Database

    Nunes, J. P. F.; Holub, Josef; Rankin, D. W. H.; Wann, D. A.; Hnyk, Drahomír

    2015-01-01

    Roč. 44, č. 26 (2015), s. 11819-11826. ISSN 1477-9226 R&D Projects: GA ČR(CZ) GAP207/11/0705 Institutional support: RVO:61388980 Keywords : NMR chemical-shifts * electron-diffraction * MP2 energy * carboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 4.197, year: 2014

  14. Charge distribution within hypercarbon-halogenated 1-Ph-2-X-1,2-dicarba-closo-dodecaboranes, (X = F, Cl, Br, I): A dipole moment and computational study

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Všetečka, V.; Drož, L.

    2010-01-01

    Roč. 978, 1-3 (2010), s. 246-249. ISSN 0022-2860 R&D Projects: GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : halogens * carboranes * dipole moments Subject RIV: CA - Inorganic Chemistry Impact factor: 1.599, year: 2010

  15. [1,2-Bis(diisopropylphosphino-1,2-dicarba-closo-dodecaborane-κ2P,P′]dichloridomercury(II

    Directory of Open Access Journals (Sweden)

    Fangfang Su

    2008-01-01

    Full Text Available In the title complex, [HgCl2(C14H38B10P2], the HgII atom is in a distorted HgCl2P2 tetrahedral coordination environment. The chelation of the Hg atom by two P atoms and two C atoms from the carborane skeleton results in a nearly planar five-membered ring.

  16. Site-specific synthesis of a hybrid boron-graphene salt.

    Science.gov (United States)

    Kahlert, Jan U; Austin, Christopher J D; Hall, Andrew J; Rawal, Aditya; Hook, James M; Rendina, Louis M; Choucair, Mohammad

    2016-01-21

    We report the first example of an ionic graphene salt containing boron. An anionic charge is introduced to the graphene surface by means of 7,8-nido-[C2B9H11](-) carborane clusters covalently and electronically bound to the graphene lattice, and this new material was isolated as its Cs(+) salt. PMID:26627051

  17. Synthesis and characterization of dicarboranylmethylammonium polyoxometalles

    Czech Academy of Sciences Publication Activity Database

    Macias, R.; Kennedy, J.D.; Bould, Jonathan; Thomton-Pett, M.

    2010-01-01

    Roč. 75, č. 11 (2010), s. 1075-1096. ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * polyoxometallates * hybrid salts Subject RIV: CA - Inorganic Chemistry Impact factor: 0.853, year: 2010

  18. Synthesis and Characterization of CptRh(PMe3)(Se2C2B10H10) in 16- and 18-Electron Half-sandwich Rhodium Complexes with 1,2-Dichalcogenolate Carborane%含有1,2-二硫(硒、碲)碳硼烷的16和18电子体系CptRh化合物的合成及表征

    Institute of Scientific and Technical Information of China (English)

    孔庆安; 金国新; 林永华

    2002-01-01

    @@ 有机半夹心结构过渡金属配位化学的研究是现代化学研究中十分活跃的一个领域[1,2].用一个6电子有机环戊二烯配体屏蔽过渡金属原子的一边,形成半夹心结构,而另一边与硫族元素配体结合形成各种结构的有机金属化合物[3~5].碳硼烷(H2C2B10H10)是由12个簇顶原子组成的球型化合物,其中2个碳原子上的氢具有一定的酸性,可与BuLi作用,形成Li2C2B10H10.元素硫(硒、碲)可定量地插入到Li-C键中,形成Li2E2C2B10H10(E=S,Se,Te,如图1).

  19. Development of a highly efficient burnable poison matrix material for cycle lifetime extension

    Energy Technology Data Exchange (ETDEWEB)

    Tulenko, J.S. [Florida Univ., 202 Nuclear Science Center, Gainesville, FL (United States); Baney, R.H.; Pressley, L. [Florida Univ., Gainesville, FL (United States)

    2001-07-01

    The University of Florida (UF) is carrying out basic research on a new class of thermally stable boron containing materials that from early indications appear to have special properties that will greatly enhance the performance of Burnable Poison Rod Assemblies (BPRA(tm)s) and address one of the major disadvantages of the use of boron shims. The new class of polymer materials, poly-acetylenic carbonyl-siloxane, termed ''Carborane'', were developed by Dr. T. Keller of the Naval Research Laboratory (NRL). Dr. T. Keller is cooperating in this research effort. Other classes of boron containing polymer materials are also under review. Displacement of water by the boron shims incurs an ''end of cycle reactivity penalty'' since at the end of cycle the moderator coefficient is strongly negative. ''Carborane'' has the property of being able to contain a tailored amount of boron while maintaining an extremely high hydrogen content, and at the same time being extremely stable to high temperatures and to neutron irradiation. Tests run by the NRL have shown that ''Carborane'' is stable to about 1000 C. The high hydrogen and carbon content contained in the ''Carborane'' Polymer offsets the large fuel cycle reactivity penalty which occurs with current generation BPRA(tm)s, as a result of the reactivity loss resulting from the BPRA(tm)s displacement of moderator water in the guide tubes of Pressurized Water Reactor (PWR) assemblies. Current generation BPRA utilize B{sub 4}C in an Al{sub 2}O{sub 3} matrix. In an attempt to minimize the reactivity penalty from water displacement, Westinghouse has developed a costly annular BPRA, called the Wet Annular Burnable Absorber (WABA) assembly. This burnable poison rod design reduces the moderator displacement by 22% by the use of a central annular water hole. The ''Carborane'' matrix proposed by the University of Florida

  20. Development of a highly efficient burnable poison matrix material for cycle lifetime extension

    International Nuclear Information System (INIS)

    The University of Florida (UF) is carrying out basic research on a new class of thermally stable boron containing materials that from early indications appear to have special properties that will greatly enhance the performance of Burnable Poison Rod Assemblies (BPRA(tm)s) and address one of the major disadvantages of the use of boron shims. The new class of polymer materials, poly-acetylenic carbonyl-siloxane, termed ''Carborane'', were developed by Dr. T. Keller of the Naval Research Laboratory (NRL). Dr. T. Keller is cooperating in this research effort. Other classes of boron containing polymer materials are also under review. Displacement of water by the boron shims incurs an ''end of cycle reactivity penalty'' since at the end of cycle the moderator coefficient is strongly negative. ''Carborane'' has the property of being able to contain a tailored amount of boron while maintaining an extremely high hydrogen content, and at the same time being extremely stable to high temperatures and to neutron irradiation. Tests run by the NRL have shown that ''Carborane'' is stable to about 1000 C. The high hydrogen and carbon content contained in the ''Carborane'' Polymer offsets the large fuel cycle reactivity penalty which occurs with current generation BPRA(tm)s, as a result of the reactivity loss resulting from the BPRA(tm)s displacement of moderator water in the guide tubes of Pressurized Water Reactor (PWR) assemblies. Current generation BPRA utilize B4C in an Al2O3 matrix. In an attempt to minimize the reactivity penalty from water displacement, Westinghouse has developed a costly annular BPRA, called the Wet Annular Burnable Absorber (WABA) assembly. This burnable poison rod design reduces the moderator displacement by 22% by the use of a central annular water hole. The ''Carborane'' matrix proposed by the University of Florida reduces the water displacement penalty by 59%, utilizing the hydrogen and carbon present in the ''Carborane''. In addition to increasing

  1. Improved synthesis of MC4-PPEA and the biological evaluation of its hydroxymethyl derivative.

    Science.gov (United States)

    Sadrerafi, Keivan; Zargham, Emilia O; Lee, Mark W

    2016-01-15

    Nicotinamide phosphoribosyltransferase (Nampt) is an intriguing target for the treatment of many diseases, including cancer. Previously, our group demonstrated that carborane clusters may be used to increase the potency of small molecule inhibitors of Nampt over other, similarly sized organic moieties. Herein, we report a greatly improved, gram-scale synthesis of our most potent agent: 1-(4'-(trans-3″-(3‴-pyridyl) acrylamide)butyl)-1,7-dicarba-closo-dodecaborane (MC4-PPEA). Additionally, the carborane moiety of the molecule has been modified with a hydroxymethyl functional group to allow for its covalent attachment to targeted prodrugs, the synthesis of which are underway. Using cell viability assays, we demonstrate that this new derivative exhibits low, to mid-nanomolar potencies against human breast cancer cell lines in vitro. PMID:26681512

  2. The Strongest Acid: Protonation of Carbon Dioxide.

    Science.gov (United States)

    Cummings, Steven; Hratchian, Hrant P; Reed, Christopher A

    2016-01-22

    The strongest carborane acid, H(CHB11F11), protonates CO2 while traditional mixed Lewis/Brønsted superacids do not. The product is deduced from IR spectroscopy and calculation to be the proton disolvate, H(CO2)2(+). The carborane acid H(CHB11F11) is therefore the strongest known acid. The failure of traditional mixed superacids to protonate weak bases such as CO2 can be traced to a competition between the proton and the Lewis acid for the added base. The high protic acidity promised by large absolute values of the Hammett acidity function (H0) is not realized in practice because the basicity of an added base is suppressed by Lewis acid/base adduct formation. PMID:26663640

  3. Caborane beam from ITEP Bernas ion source for semiconductor implanters

    Energy Technology Data Exchange (ETDEWEB)

    Seleznev, D.; Hershcovitch, A.; Kropachev, G.; Kozlov, A.; Kuibeda, R.; Koshelev, V.; Kulevoy, T.; Jonson, B.; Poole, J.; Alexeyenko, O.; Gurkova, E.; Oks, E.; Gushenets, V.; Polozov, S.; Masunov, E.

    2010-02-01

    A joint research and development of steady state intense boron ion sources for hundreds of electron-volt ion implanters has been in progress for the past 5 years. The difficulties of extraction and transportation of low energy boron beams can be solved by implanting clusters of boron atoms. In Institute for Theoretical and Experimental Physics (ITEP) the Bernas ion source successfully generated the beam of decaborane ions. The carborane (C{sub 2}B{sub 10}H{sub 12}) ion beam is more attractive material due to its better thermal stability. The results of carborane ion beam generation are presented. The result of the beam implantation into the silicon wafer is presented as well.

  4. Di-μ-thiocyanato-bis{[1,2-bis(diisopropylphosphanyl-1,2-dicarba-closo-dodecaborane]silver(I}

    Directory of Open Access Journals (Sweden)

    Dacheng Li

    2011-01-01

    Full Text Available The title compound, [Ag2(NCS2(C14H38B10P22], was synthesized by the reaction of 1,2-bis(diisopropylphosphanyl-1,2-dicarba-closo-dodecaborane with AgSCN. The diisopropylphosphanyl-closo-carborane ligand is coordinated in a bidentate manner to the AgI atom through the two P atoms. The coordination of the AgI atom is distorted tetrahedral, in which two vertices are formed by the P atoms of the chelating diphosphine ligand, and the other two are occupied by the S and N atoms of the two bridging thiocyanate anions, leading to a centrosymmetric binuclear complex. The distance between the two C atoms in the carborane skeleton is 1.851 (6 Å.

  5. (1,2-Dicarba-closo-dodecaboranyltrimethylmethanaminium iodide

    Directory of Open Access Journals (Sweden)

    Jong-Dae Lee

    2011-08-01

    Full Text Available The title compound, [1-(CH33NCH2-1,2-C2B10H11]+·I− or C6H22B10N+·I−, was obtained by the reaction of (1,2-dicarba-closo-dodecaboranyldimethylmethanamine with methyl iodide. The asymmetric unit contains two iodide anions and two (o-carboranyltetramethylammonium cations. The bond lengths and angles in the carborane cage are within normal ranges, but the N—Cmethylene—Ccage angle is very large [120.2 (2°] because of repulsion between the carborane and tetramethylammonium units. In the crystal, ions are linked through C—H...I hydrogen bonds.

  6. Use of Li.sub.2[B.sub.12H.sub.12] salt to absorb water into polymers

    Energy Technology Data Exchange (ETDEWEB)

    Eastwood, Eric A.; Bowen, III, Daniel E.

    2016-08-30

    Methods of adjusting the properties of a composition are provided. The compositions comprise a polymer-containing matrix and a filler comprising a hygroscopic salt. Preferred such salts comprise a cage compound selected from the group consisting of borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer.

  7. Synthesis of novel C-(o-carboranyl)-2-deoxy-d-ribose conjugates

    Czech Academy of Sciences Publication Activity Database

    Šnajdr, I.; Janoušek, Z.; Kotora, Martin

    Praha: Institute of Organic Chemistry and Biochemistry AS CR, v. v. i., 2011 - (Hocek, M.), s. 465-466. (Collection Symposium Series. 12). ISBN 978-80-86241-37-1. [Chemistry of Nucleic Acid Components /15./. Český Krumlov (CZ), 05.06.2011-10.06.2011] Institutional research plan: CEZ:AV0Z40550506 Keywords : carboranes * nucleosides * alkynes Subject RIV: CC - Organic Chemistry

  8. Boron Clusters as Highly Stable Magnesium-Battery Electrolytes**

    OpenAIRE

    Carter, Tyler J; Mohtadi, Rana; Arthur, Timothy S; Mizuno, Fuminori; Zhang, Ruigang; Shirai, Soichi; Kampf, Jeff W.

    2014-01-01

    Boron clusters are proposed as a new concept for the design of magnesium-battery electrolytes that are magnesium-battery-compatible, highly stable, and noncorrosive. A novel carborane-based electrolyte incorporating an unprecedented magnesium-centered complex anion is reported and shown to perform well as a magnesium-battery electrolyte. This finding opens a new approach towards the design of electrolytes whose likelihood of meeting the challenging design targets for magnesium-battery electro...

  9. Program and Abstracts, Boron Americas IX Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Feakes, Debra A.

    2006-08-09

    The Scientific and Technical Information (STI) submitted includes the final report and a collection of abstracts for the Ninth Boron in the Americas Conference which was held May 19-22, 2004, in San Marcos, Texas. The topics covered in the abstracts include: Application in Medicine, Application in Organic Synthesis and Catalysis, Boranes and Carboranes, Materials and Polymers, Metallaboranes and Metallacarboranes, Organoboron Compounds, Synthesis and Catalysis, and Theoretical Studies. Attendees represented researchers from government, industry, and academia.

  10. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Czech Academy of Sciences Publication Activity Database

    Selucký, P.; Rais, J.; Lučaníková, M.; Grüner, Bohumír; Kvíčalová, Magdalena; Fejfarová, Karla; Císařová, I.

    2008-01-01

    Roč. 96, 4-5 (2008), s. 273-284. ISSN 0033-8230 R&D Projects: GA MŠk LC523 Grant ostatní: GA ČR(CZ) GA104/08/0006 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z10100521 Keywords : carboranes * metallaboranes * dicarbollides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.084, year: 2008

  11. The sixteen CB11HnMe12-n - anions with fivefold substitution symmetry: Anodic oxidation and electronic strycture

    Czech Academy of Sciences Publication Activity Database

    King, B. T.; Körbe, Stefanie; Schreiber, P. J.; Clayton, J.; Němcová, Adriana; Havlas, Zdeněk; Vyakaranam, K.; Fete, M. G.; Zharov, I.; Ceremuga, J.; Michl, Josef

    2007-01-01

    Roč. 129, č. 43 (2007), s. 12960-12980. ISSN 0002-7863 R&D Projects: GA MŠk ME 857 Grant ostatní: NSF(US) CHE-0446688; NSF(US) OISE-0532040 Institutional research plan: CEZ:AV0Z40550506 Keywords : carborane clusters * methylation * electrooxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 7.885, year: 2007

  12. Cobalt bis(dicarbollides)(1-) covalently attached to the calix[4]arene platform: The first combination of organic bowl-shaped matrices and inorganic metallaborane cluster anions

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Mikulášek, Libor; Báča, Jiří; Císařová, I.; Böhmer, V.; Danila, C.; Reinoso-García, M.M.; Verboom, W.; Reinhoudt, D.N.; Casnati, A.; Ungaro, R.

    -, č. 10 (2005), s. 2022-2039. ISSN 1434-193X R&D Projects: GA MŠk(CZ) LC523; GA AV ČR KSK4050111 Grant ostatní: EEC(XE) F16W-CT-2003-508854 Institutional research plan: CEZ:AV0Z40320502 Keywords : calixarenes * carboranes * dicarbollides Subject RIV: CA - Inorganic Chemistry Impact factor: 2.548, year: 2005

  13. RETARDANTY HOŘENÍ, JEJICH POUŽITÍ A VLIV NA ŽIVOTNÍ PROSTŘEDÍ

    OpenAIRE

    Petrová, Š. (Šárka); Soudek, P. (Petr); Vaněk, T. (Tomáš)

    2015-01-01

    Fire is a common cause of damage to people and property. The fires also cause a wide variety of acute and chronic pollution due to acid gases and persistent organic chemicals. Flame retardants are highly required chemicals that improve thermal resistance of materials. Main types of fire retardants used in polymers are phosphines, phosphonates, phosphates, silanes, siloxanes, boric acid, borates, carboranes, melamine derivatives, Al and Mg hydroxides as well as nanomaterials. Generally...

  14. Skeletal Alkylcarbonation (SAC) Reactions as a Simple Design for Cluster-Carbon Insertion and Cross-Coupling: High-Yield Access to Substituted Tricarbollides from 6,9-Dicarba-arachno-decaborane(14)

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil; Bakardjiev, Mario; Holub, Josef; Růžička, A.; Padělková, Z.; Olejník, R.; Švec, Petr

    2011-01-01

    Roč. 17, č. 47 (2011), s. 13156-13159. ISSN 0947-6539 R&D Projects: GA MŠk LC523; GA ČR(CZ) GAP207/11/0705 Institutional research plan: CEZ:AV0Z40320502 Keywords : acyl chlorides * boranes * carboranes * cross-coupling * synthetic method s Subject RIV: CA - Inorganic Chemistry Impact factor: 5.925, year: 2011

  15. Additive Character of Electron Donation by Methyl Substituents within a Complete Series of Polymethylated [1-(eta(6)-Me(n)C(6)H(6-n))-closo-1,2,3-FeC(2)B(9)H(11)] Complexes. Linear Correlations of the NMR Parameters and Fe(II/III) Redox Potentials with the Number of Arene Methyls

    Czech Academy of Sciences Publication Activity Database

    Štíbr, Bohumil; Bakardjiev, Mario; Holub, Josef; Růžička, A.; Padělková, Z.; Štěpnička, P.

    2011-01-01

    Roč. 50, č. 7 (2011), s. 3097-3102. ISSN 0020-1669 R&D Projects: GA MŠk LC523; GA ČR(CZ) GAP207/11/0705 Institutional research plan: CEZ:AV0Z40320502 Keywords : organotransition-metal metallacarboranes * molecular-structure * crystal-structures * iron * carborane Subject RIV: CA - Inorganic Chemistry Impact factor: 4.601, year: 2011

  16. Improved synthesis of [closo-1-CB9H10 ](-) anion and new c-substituted derivatives

    Czech Academy of Sciences Publication Activity Database

    Ringstrand, B.; Bateman, D.; Shoemaker, R. K.; Janoušek, Zbyněk

    2009-01-01

    Roč. 74, č. 3 (2009), s. 419-431. ISSN 0010-0765 R&D Projects: GA MŠk LC523; GA MŠk ME 857 Grant ostatní: NSF(US) CHE-0446688; NSF(US) OISE-0532040 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * carboranes * monocarbaborane anions Subject RIV: CA - Inorganic Chemistry Impact factor: 0.856, year: 2009

  17. Synthesis of Periphery-Decorated and Core-Initiated Borane Polyanionic Macromolecules.

    Science.gov (United States)

    Teixidor, Francesc; Pepiol, Ariadna; Viñas, Clara

    2015-07-20

    A new class of globular polybranched macromolecules that contain multiple anionic metallacarborane clusters at the o-carborane periphery is reported. The water soluble high boron rich containing molecules could be of interest for boron neutron capture therapy (BNCT) as well as for drug delivery. The reinforced electrostatic noncovalent interactions between anionic polyethylene glycol cobaltabisdicarbollide (PEG-COSAN) branches and the ammonium cation have been shown using ESI-MS. PMID:26096811

  18. Use of novel metalloporphyrins as imageable tumor-targeting agents for radiation therapy

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Slatkin, Daniel N.

    2005-10-04

    The present invention covers halogenated derivatives of boronated phorphyrins containing multiple carborane cages having the formula ##STR1## which selectively accumulate in neoplastic tissue within the irradiation volume and thus can be used in cancer therapies including, but not limited to, boron neutron-capture therapy and photodynamic therapy. The present invention also covers methods for using these halogenated derivatives of boronated porphyrins in tumor imaging and cancer treatment.

  19. Molecular ion sources for low energy semiconductor ion implantation (invited)

    Energy Technology Data Exchange (ETDEWEB)

    Hershcovitch, A., E-mail: hershcovitch@bnl.gov [Brookhaven National Laboratory, Upton, New York 11973 (United States); Gushenets, V. I.; Bugaev, A. S.; Oks, E. M.; Vizir, A.; Yushkov, G. Yu. [High Current Electronics Institute, Siberian Branch of Russian Academy of Sciences, Tomsk 634055 (Russian Federation); Seleznev, D. N.; Kulevoy, T. V.; Kozlov, A.; Kropachev, G. N.; Kuibeda, R. P.; Minaev, S. [Institute for Theoretical and Experimental Physics, Moscow 117218 (Russian Federation); Dugin, S.; Alexeyenko, O. [State Scientific Center of the Russian Federation State Research Institute for Chemistry and Technology of Organoelement Compounds, Moscow (Russian Federation)

    2016-02-15

    Smaller semiconductors require shallow, low energy ion implantation, resulting space charge effects, which reduced beam currents and production rates. To increase production rates, molecular ions are used. Boron and phosphorous (or arsenic) implantation is needed for P-type and N-type semiconductors, respectively. Carborane, which is the most stable molecular boron ion leaves unacceptable carbon residue on extraction grids. A self-cleaning carborane acid compound (C{sub 4}H{sub 12}B{sub 10}O{sub 4}) was synthesized and utilized in the ITEP Bernas ion source resulting in large carborane ion output, without carbon residue. Pure gaseous processes are desired to enable rapid switch among ion species. Molecular phosphorous was generated by introducing phosphine in dissociators via 4PH{sub 3} = P{sub 4} + 6H{sub 2}; generated molecular phosphorous in a pure gaseous process was then injected into the HCEI Calutron-Bernas ion source, from which P{sub 4}{sup +} ion beams were extracted. Results from devices and some additional concepts are described.

  20. Characterization of a boron carbide-based polymer neutron sensor

    Science.gov (United States)

    Tan, Chuting; James, Robinson; Dong, Bin; Driver, M. Sky; Kelber, Jeffry A.; Downing, Greg; Cao, Lei R.

    2015-12-01

    Boron is used widely in thin-film solid-state devices for neutron detection. The film thickness and boron concentration are important parameters that relate to a device's detection efficiency and capacitance. Neutron depth profiling was used to determine the film thicknesses and boron-concentration profiles of boron carbide-based polymers grown by plasma enhanced chemical vapor deposition (PECVD) of ortho-carborane (1,2-B10C2H12), resulting in a pure boron carbide film, or of meta-carborane (1,7-B10C2H12) and pyridine (C5H5N), resulting in a pyridine composite film, or of pyrimidine (C4H4N2) resulting in a pure pyrimidine film. The pure boron carbide film had a uniform surface appearance and a constant thickness of 250 nm, whereas the thickness of the composite film was 250-350 nm, measured at three different locations. In the meta-carborane and pyridine composite film the boron concentration was found to increase with depth, which correlated with X-ray photoelectron spectroscopy (XPS)-derived atomic ratios. A proton peak from 14N (n,p)14C reaction was observed in the pure pyrimidine film, indicating an additional neutron sensitivity to nonthermal neutrons from the N atoms in the pyrimidine.

  1. Synthesis and 11C-Radiolabelling of 2-Carboranyl Benzothiazoles

    Directory of Open Access Journals (Sweden)

    Kiran B. Gona

    2015-04-01

    Full Text Available Dicarba-closo-dodecaboranes, commonly known as carboranes, possess unique physico-chemical properties and can be used as hydrophobic moieties during the design of new drugs or radiotracers. In this work, we report the synthesis of two analogues of 2-(4-aminophenylbenzothiazole (a compound that was found to elicit pronounced inhibitory effects against certain breast cancer cell lines in vitro in which the phenyl ring has been substituted by a m-carborane cage. Two different synthetic strategies have been used. For the preparation of 1-(9-amino-1,7-dicarba-closo-dodecaboran-1-yl-benzo-thiazole, the benzothiazole group was first introduced on one of the cluster carbon atoms of m-carborane and the amine group was further attached in three steps. For the synthesis of 1-(9-amino-1,7-dicarba-closo-dodecaboran-1-yl-6-hydroxybenzothiazole, iodination was performed before introducing the benzothiazole group, and the amino group was subsequently introduced in six steps. Both compounds were radiolabelled with carbon-11 using [11C]CH3OTf as the labelling agent. Radiolabelling yields and radiochemical purities achieved should enable subsequent in vitro and in vivo investigations.

  2. Synthesis of globular precursors.

    Science.gov (United States)

    Teixidor, Francesc; Sillanpää, Reijo; Pepiol, Ariadna; Lupu, Marius; Viñas, Clara

    2015-09-01

    o-Carborane (C2 B10 H12 ) was adapted to perform as the core of globular macromolecules, dendrons or dendrimers. To meet this objective, precisely defined substitution patterns of terminal olefin groups on the carborane framework were subjected to Heck cross-coupling reactions or hydroboration leading to hydroxyl terminated arms. These led to new terminal groups (chloro, bromo, and tosyl leaving groups, organic acid, and azide) that permitted ester production, click chemistry, and oxonium ring opening to be performed as examples of reactions that demonstrate the wide possibilities of the globular icosahedral carboranes to produce new dendritic or dendrimer-like structures. Polyanionic species were obtained in high yield through the ring-opening reaction of cyclic oxonium compound [3,3'-Co(8-C4 H8 O2 -1,2-C2 B9 H10 )(1',2'-C2 B9 H11 )] by using terminal hydroxyl groups as nucleophiles. These new polyanionic compounds that contain multiple metallacarborane clusters at their periphery may prove useful as new classes of compounds for boron neutron capture therapy with enhanced water solubility and as cores to make a new class of high-boron globular macromolecules. PMID:26228947

  3. B-H···π Interaction: A New Type of Nonclassical Hydrogen Bonding.

    Science.gov (United States)

    Zhang, Xiaolei; Dai, Huimin; Yan, Hong; Zou, Wenli; Cremer, Dieter

    2016-04-01

    For the first time, nonclassical hydrogen (H)-bonding involving a B-H···π interaction is described utilizing both quantum chemical predictions and experimental realization. In the gas phase, a B-H···π H-bond is observed in either B2H6···benzene (ΔE = -5.07 kcal/mol) or carborane···benzene (ΔE = -3.94 kcal/mol) complex at reduced temperatures. Ir-dimercapto-carborane complexes [Cp*Ir(S2C2B10H10)] are designed to react with phosphines PR3 (R = C6H4X, X = H, F, OMe) to give [Cp*Ir(PR3)S2C2B10H10] for an investigation of B-H···π interactions at ambient temperatures. X-ray diffraction studies reveal that the interaction between the carborane BH bonds and the phosphine aryl substituents involves a BH···π H-bond (H···π distance: 2.40-2.76 Å). (1)H NMR experiments reveal that B-H···π interactions exist in solution according to measured (1)H{(11)B} signals at ambient temperatures in the range 0.0 ≤ δ ≤ 0.3 ppm. These are high-field shifted by more than 1.5 ppm relative to the (1)H{(11)B} signals obtained for the PMe3 analog without B-H···π bonding. Quantum chemical calculations suggest that the interaction is electrostatic and the local (B)H···ring stretching force constant is as large as the H-bond stretching force constant in the water dimer. PMID:26910602

  4. A Novel Boron-Loaded Liquid Scintillator for Neutron Detection

    OpenAIRE

    Sur, B.; Li, L.; E. Pruszkowski; Dai, X.; G. Bentoumi

    2012-01-01

    A boron-loaded liquid scintillator (LS) has been optimized for neutron detection application in a high gamma field environment. It is composed of the solvent linear alkylbenzene (LAB), a boroncontaining material, o-carborane (C2B10H12); a fluor, 2,5-diphenyloxazole (PPO); and a wavelength shifter, 1,4-bis[2-methylstyryl] benzene (bis-MSB). Preparation of the liquid scintillator and optimization of its chemical composition are described. The boronloaded LS has been tested with a neutron beam a...

  5. Molecular Ion Beam Transportation for Low Energy Ion Implantation

    International Nuclear Information System (INIS)

    A joint research and development of steady state intense boron ion sources for 100's of electron-volt ion implanters has been in progress for the past five years. Current density limitation associated with extracting and transporting low energy ion beams result in lower beam currents that in turn adversely affects the process throughput. The transport channel with electrostatic lenses for decaborane (B10H14) and carborane (C2B10H12) ion beams transportation was developed and investigated. The significant increase of ion beam intensity at the beam transport channel output is demonstrated. The transport channel simulation, construction and experimental results of ion beam transportation are presented.

  6. Boron-loaded plastic scintillator with neutron-γ pulse shape discrimination capability

    International Nuclear Information System (INIS)

    Development of the plastic scintillator with neutron sensitivity from thermal to multi-MeV and pulse shape discrimination (PSD) has been demonstrated. Incorporation of 10B-containing compounds into the plastic scintillator with PSD capability leads to detector improvement in regard to neutron detection efficiency while preserving the discrimination between neutrons and γ-rays. Effects of boron loading on scintillation and pulse shape discrimination properties are discussed. A PSD figure-of-merit value of 1.4±0.03 has been achieved for events in a thermal neutron energy domain, 50–100 keVee, for PSD plastic loaded with 5 wt.% of m-carborane

  7. Numerical Sequence of Borane Series

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2014-09-01

    Full Text Available A table of hydroborane families has been created. The table links boranes of different families(homologous series and members of the same family based on k number. The table is useful deducing straight away whether a borane( molecular formula is closo, nido or arachno or something else. The table also indicates that boranes are formed according to natural periodic function (arithmetical progression. The empirical formula utilized is extremely versatile, simple and based on the principle of Nobel gas configuration. It could be used in both simple and complex boranes and carboranes. The closo members which portray characteristic shapes also have characteristic k1 numbers.

  8. Synthesis of functionalized cobaltacarboranes based on the closo-[(1,2-C2B9H11)(2)-3,3 '-Co](-) ion bearing polydentate ligands for separation of M3+ cations from nuclear waste solutions. Electrochemical and liquid-liquid extraction study of selective transfer of M3+ metal cations to an organic phase. Molecular structure of the closo-[(8-(2-CH3O-C5H4-O)-(CH2CH2O)(2)-1,2-C2B9H10)-(1 ',2 '-C2B9H11)-3,3 '-Co]Na determined by X-ray diffraction analysis

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Grüner, Bohumír; Heřmánek, Stanislav; Báča, Jiří; Mareček, Vladimír; Jänchenová, Hana; Lhotský, Alexandr; Holub, Karel; Selucký, P.; Rais, J.; Císařová, I.; Čáslavský, Josef

    2002-01-01

    Roč. 21, 9-10 (2002), s. 975-986. ISSN 0277-5387 R&D Projects: GA MŠk LN00A028; GA MŠk LB98233; GA ČR GA104/01/0142; GA ČR GA203/99/M037; GA ČR GA104/99/1096 Institutional research plan: CEZ:AV0Z4032918 Keywords : carboranes * carba metallaboranes * dicarbollides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.414, year: 2002

  9. Boronated porphyrins in NCT: Results with a new potent tumor localizer

    International Nuclear Information System (INIS)

    Several chemical methods are available for the solubilization of boronated porphyrins. We have previously reported the tumor localization of nido carboranyl porphyrins in which the icosahedral carborane cages have been opened to give B9C2 anions. One of these species has shown tumor boron levels of nearly 50 μg B/g when delivered by week-long subcutaneous infusions. We report here recent in vivo experiments with a new, highly water-soluble porphyrin based on the hematoporphyrin-type of compound in which aqueous solubility is achieved using the two propionic acid side chains of the ''natural'' porphyrin frame. 7 refs

  10. Boron carbide-based ceramics via polymer route synthesis

    International Nuclear Information System (INIS)

    Boron carbide is a ceramic material with excellent high temperature physical properties. As compared to conventional techniques, the preparation of boron carbide from polymeric precursors is attractive as this technique offers a number of unique advantages. In this paper, the screening of polymeric precursors to boron carbide will be discussed. Two promising boron carbide, carborane containing polymeric precursors have resulted in 60-70 wt.% ceramic yields. The chemistry of polymer synthesis and the transformations from the polymer to amorphous and crystalline boron carbide were investigated with infrared spectroscopy, NMR spectroscopy, thermal analysis, and x-ray diffraction

  11. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of ico-sahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  12. The coadsorption and interaction of molecular icosahedra with mercury

    Energy Technology Data Exchange (ETDEWEB)

    Ilie, C.C.; Balaz, S.; Rosa, L.G.; Doudin, B.; Dowben, P.A. [University of Nebraska - Lincoln, Department of Physics and Astronomy and the Center for Materials Research and Analysis, Behlen Laboratory of Physics, Lincoln, NE (United States); Zhang, J. [Florida International University, Department of Physics, Miami, FL (United States); University of Nebraska - Lincoln, Center for Materials Research and Analysis, 116 Brace Laboratory, Lincoln, NE (United States); Lunca-Popa, P. [University of Nebraska - Lincoln, Department of Physics and Astronomy and the Center for Materials Research and Analysis, Behlen Laboratory of Physics, Lincoln, NE (United States); University of Nebraska - Lincoln, College of Engineering and Technology, N104 Walter Scott Engineering Center, 17th and Vine Streets, Lincoln, NE (United States); Bianchetti, C.; Tittsworth, R. [Louisiana State University, J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Baton Rouge, LA (United States); Brand, J.I. [University of Nebraska - Lincoln, College of Engineering and Technology, N104 Walter Scott Engineering Center, 17th and Vine Streets, Lincoln, NE (United States)

    2005-12-01

    We have investigated the changes in the electronic structure of molecularly adsorbed orthocarborane films, as a function of Hg co-adsorption, using photoemission. The interaction between Hg and molecular orthocarborane is weak and results in the formation of some small aggregates of Hg. This behavior is very different from alkali metals interaction with molecular carborane films and the interaction of Hg with semiconducting boron carbide films. Hg doping of semiconducting boron carbide may decrease the activation barrier for intrinsic carrier mobility, but does not significantly increase the number of carriers. (orig.)

  13. Anionic and zwitterionic carboranyl N-heterocyclic carbene Au(i) complexes.

    Science.gov (United States)

    Fisher, Steven P; El-Hellani, Ahmad; Tham, Fook S; Lavallo, Vincent

    2016-06-14

    The syntheses of the first carboranyl N-heterocyclic carbene complexes with transition metals are reported. Both unsymmetrical mono-anionic and symmetrical dianionic NHCs readily react with ClAuSMe2 to afford unusual zwitterionic and anionic Au(i) dimethyl sulfide adducts. The compounds are characterized by NMR, mass spectrometry, and single crystal X-ray diffraction studies. Percent buried volume (%Vbur) calculations indicate that replacement of an adamantyl group by a hydride substituted icosahedral carborane anion results in a 3.7% increase in %Vbur. PMID:26922968

  14. Conjugation between σ- and π-Aromaticity in 1-C-Arylated Monocarba-closo-dodecaborate Anions.

    Science.gov (United States)

    Otsuka, Mai; Takita, Ryo; Kanazawa, Junichiro; Miyamoto, Kazunori; Muranaka, Atsuya; Uchiyama, Masanobu

    2015-12-01

    Conjugation between σ- and π-aromatic moieties in 1-C-arylated monocarba-closo-dodecaborate anion derivatives 2 has been identified by means of kinetic experimental studies combined with theoretical calculations. We found that the reaction rate of iodination at the 12-B vertex of the carborane anion cage was affected by distal substituents on the benzene ring connected at the antipodal carbon vertex. Hammett and Yukawa-Tsuno plots indicated that substantial resonance effects are involved. Density functional theory calculations enabled detailed interpretation of the electronic interaction. PMID:26584675

  15. Inner-shell excitation and ionic fragmentation of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Hitchcock, A.P.; Tyliszczak, T. [McMaster Univ., Hamilton, Ontario (Canada); Cavell, R.G. [Univ. of Alberta, Edmonton (Canada)] [and others

    1997-04-01

    Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can reveal cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.

  16. Design of hybrid conjugated polymer materials: 1) Novel inorganic/organic hybrid semiconductors and 2) Surface modification via grafting approaches

    Science.gov (United States)

    Peterson, Joseph J.

    The research presented in this dissertation focuses on the design and synthesis of novel hybrid conjugated polymer materials using two different approaches: (1) inorganic/organic hybrid semiconductors through the incorporation of carboranes into the polymer structure and (2) the modification of surfaces with conjugated polymers via grafting approaches. Hybrid conjugated polymeric materials, which are materials or systems in which conjugated polymers are chemically integrated with non-traditional structures or surfaces, have the potential to harness useful properties from both components of the material to help overcome hurdles in their practical realization in polymer-based devices. This work is centered around the synthetic challenges of creating new hybrid conjugated systems and their potential for advancing the field of polymer-based electronics through both greater understanding of the behavior of hybrid systems, and access to improved performance and new applications. Chapter 1 highlights the potential applications and advantages for these hybrid systems, and provides some historical perspective, along with relevant background materials, to illustrate the rationale behind this work. Chapter 2 explores the synthesis of poly(fluorene)s with pendant carborane cages. The Ni(0) dehalogenative polymerization of a dibromofluorene with pendant carborane cages tethered to the bridging 9-position produced hybrid polymers produced polymers which combined the useful emissive characteristics of poly(fluorene) with the thermal and chemical stability of carborane cages. The materials were found to display increased glass transition temperatures and showed improved emission color stability after annealing at high temperatures relative to the non-hybrid polymer. The design and synthesis of a poly(fluorene)-based hybrid material with carborane cages in the backbone, rather than as pendant groups, begins in chapter 3. Poly(fluorene) with p-carborane in the backbone is

  17. Carbon monoxide protonation in condensed phases and bonding to surface superacidic Brønsted centers.

    Science.gov (United States)

    Stoyanov, Evgenii S; Malykhin, Sergei E

    2016-02-14

    Using infrared (IR) spectroscopy and density functional theory (DFT) calculations, interaction of CO with the strongest known pure Brønsted carborane superacids, H(CHB11Hal11) (Hal = F, Cl), was studied. CO readily interacted at room temperature with H(CHB11F11) acid, forming a mixture of bulk salts of formyl and isoformyl cations, which were in equilibrium An(-)H(+)CO COH(+)An(-). The bonding of CO to the surface Brønsted centers of the weaker acid, H(CHB11Cl11), resulted in breaking of the bridged H-bonds of the acid polymers without proton transfer (PT) to CO. The binding occurred via the C atom (blue shift ΔνCO up to +155-167 cm(-1), without PT) or via O atom (red shift ΔνCO up to -110 cm(-1), without PT) always simultaneously, regardless of whether H(+) is transferred to CO. IR spectra of all species were interpreted by B3LYP/cc-pVQZ calculations of the simple models, which adequately mimic the ability of carborane acids to form LH(+)CO, LH(+)CO, COH(+)L, and COH(+)L compounds (L = bases). The CO bond in all compounds was triple. Acidic strength of the Brønsted centers of commonly used acid catalysts, even so-called superacidic catalysts, is not sufficient for the formation of the compounds studied. PMID:26805010

  18. First gaseous boronization during pulsed discharge cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Ko, J., E-mail: jinseok@nfri.re.kr [Department of Physics, University of Wisconsin, Madison, WI (United States); Den Hartog, D.J.; Goetz, J.A.; Weix, P.J.; Limbach, S.T. [Department of Physics, University of Wisconsin, Madison, WI (United States)

    2013-01-15

    The first successful gaseous boronization during a pulsed discharge is reported. Sublimation of o-carborane (C{sub 2}B{sub 10}H{sub 12}) combined with pulsed discharge plasmas with a repetition rate of 1 Hz is used to produce a hard boron-containing coating for reversed field pinch (RFP) plasmas in the Madison Symmetric Torus. X-ray photoelectron spectroscopy with Ar ion beam etching for silicon coupons installed at the plasma boundary shows about 60% boron concentration in the deposited layer. Both profilometer and scanning electron microscope analyses of the silicon coupons imply a strong toroidally non-uniform deposition depending on the location of the o-carborane injection. The layer thickness ranges from 50 to 300 nm. Ellipsometry calibrated with the profilometer results yields a refractive index of 2.2-2.3 for the films. The high refractive index implies that the coating is hard and has a well-ordered morphology. A reduction in wall recycling has consistently been observed after all boronization sessions. Comparison of the X-ray spectra in standard RFP plasmas before and after boronization indicates a slight decrease in the effective ionic charge.

  19. A wide energy neutron dosimeter from thermal to fast based on CR-39 SSNTD

    International Nuclear Information System (INIS)

    CR-39 PADC (poly-allyl-diglycol carbonate) detector is presently being used for fast neutron (>100 keV) monitoring of the radiation workers involved in nuclear reactors, reprocessing plants and well-oil logging industries. It is insensitive to beta and gamma radiation in a wide range of doses. CR-39 is polymerized with 0.1% Di-octyl Phthalate (DOP) as plasticizer and 3.3% isopropyl peroxy dicarbonate (IPP) as initiator. The Allyl Diglycol Carbonate monomer, if doped with 0.5% carborane (B10H10C2H2), its sensitivity to thermal neutrons is enhanced due to 10B(n, α)7Li reaction. This paper presents response of boron doped CR-39 and normal CR-39 (without boron doping) to fast and thermal neutrons

  20. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center.

    Science.gov (United States)

    Eleazer, Bennett J; Smith, Mark D; Popov, Alexey A; Peryshkov, Dmitry V

    2016-08-24

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes. PMID:27526855

  1. Graph theory in the study of metal cluster bonding topology: applications to metal clusters having fused polyhedra

    International Nuclear Information System (INIS)

    The energy levels in a delocalized two- or three-dimensional chemical structure are related to the eigenvalues of the graph representing the corresponding bonding topology. Such relatively crude but computationally undemanding graph theory-derived models provide a clear demonstration of the close relationship between two-dimensional aromatic systems such as benzene and three-dimensional aromatic systems such as deltahedral boranes, carboranes, and metal clusters. The basic building blocks for the three-dimensional aromatic systems are deltahedra, having no degree 3 vertices. Delocalized bonding in such systems having v vertices requires two electrons for a multicenter core bond as well as 2v electrons for pairwise surface bonding. A problem of particular interest is how metal cluster polyhedra can fuse together, leading ultimately to the infinite structures of the bulk metals. As a model for such processes the fusion of rhodium carbonyl octahedra is examined using graph theory

  2. Enhanced Plasma Performance by ICRF Boronization

    Institute of Scientific and Technical Information of China (English)

    万宝年; 赵燕平; 李建刚; 宋梅; 吴振伟; 罗家融; 李成富; 王小明

    2002-01-01

    Boronization with carborane (C2B10H12) by ICRF has been applied routinely to the walls of HT-7 super-conducting tokamak for the reduction of impurity influx, especially carbon and oxygen. Significant suppression of metallic impurities and radiating power fraction are achieved. The improved confinement for both particle and energy is observed in full range of operation parameters. Energy balance analysis shows that electron heat diffusion coefficient is strongly reduced. Measurements by Langmuir probes at the edge plasma show that the poloidal velocity shear after boronization is changed to a profile favoring to good confinement. The main emphasis of this paper is to describe effects of boronization on aspects of the enhanced plasma performance.

  3. The Effect of Amorphization Conditions on the Measured Activation of Source Drain Extension Implants

    International Nuclear Information System (INIS)

    Un-patterned wafers were processed using low-dose Indium or medium-dose Germanium pre-amorphization implants (PAI) followed by p-type dopant implants of BF2 or carborane (CBH). The wafers were then annealed by RTA (spike), laser anneal (LSA) or combination of LSA and spike. Active dopant distributions calculated from SIMS and sheet resistance measurements compared favorably with those determined by differential Hall, which is a challenging technique for shallow profiles. The trends in B diffusion behavior and activation are discussed in relation to the different implant damage budgets, damage evolution during the anneals and presence of fluorine. In particular, for low thermal budget LSA only anneals, CBH implants appear to give higher activation than BF2 due to the absence of fluorine.

  4. Synthesis and comparative toxicology of a series of polyhedral borane anion-substituted tetraphenyl porphyrins.

    Science.gov (United States)

    Koo, Myoung-Seo; Ozawa, Tomoko; Santos, Raquel A; Lamborn, Kathleen R; Bollen, Andrew W; Deen, Dennis F; Kahl, Stephen B

    2007-02-22

    Three structurally similar tetraphenylporphyrins bearing polyhedral borane anions have been synthesized and their toxicological profiles obtained in rats. These conjugates were found to have quite different acute toxicities as manifested at the maximum tolerated dose (MTD). When given at the MTD and observed over 28 days, the most acutely toxic porphyrin was found to be devoid of toxicity, as measured by blood chemistry panels. The remaining two less acutely toxic compounds both elicited significant changes, characterized by moderate to severe thrombocytopenia, failure to gain weight normally and changes in liver enzymes indicative of mild hepatotoxicity. All toxic effects were transient, with platelets rebounding to above normal levels at day 28. We conclude that thrombocytopenia is the dose limiting toxicity for boronated porphyrins in mammals and suggest that these effects may be due to the porphyrin, not the borane or carborane. PMID:17253677

  5. Program for BNCT with accelerator-produced keV neutrons and related chemical and biological studies

    International Nuclear Information System (INIS)

    Boron neutron capture therapy (BNCT), with slow neutrons, is based on the large cross-section of the stable boron isotope, 10B, for the thermal neutron capture. Upon capture of a neutron, the 10B nucleus is transformed to a highly excited 11B compound nucleus that promptly disintegrates into two antiparallel, highly energetic and cell-killing fragments, one 4He2+ and one 7Li3+ ion, with ranges of 9 and 5 micrometers, respectively. By more or less selective accumulation of 10B in suitable chemical form in or in close contact with the target cells, the probability of target cell sterilization is significantly increased, after therapeutic slow-neutron irradiation. This paper summarizes four different studies. They are: a spallation source for BNCT; boronation of EGF via dextran; synthesis of carboranes containing amino groups; and analysis of boron compounds with ICP-MS

  6. Boron clusters in luminescent materials.

    Science.gov (United States)

    Mukherjee, Sanjoy; Thilagar, Pakkirisamy

    2016-01-21

    In recent times, luminescent materials with tunable emission properties have found applications in almost all aspects of modern material sciences. Any discussion on the recent developments in luminescent materials would be incomplete if one does not account for the versatile photophysical features of boron containing compounds. Apart from triarylboranes and tetra-coordinate borate dyes, luminescent materials consisting of boron clusters have also found immense interest in recent times. Recent studies have unveiled the opportunities hidden within boranes, carboranes and metalloboranes, etc. as active constituents of luminescent materials. From simple illustrations of luminescence, to advanced applications in LASERs, OLEDs and bioimaging, etc., the unique features of such compounds and their promising versatility have already been established. In this review, recent revelations about the excellent photophysical properties of such materials are discussed. PMID:26574714

  7. Stealth Amphiphiles: Self-Assembly of Polyhedral Boron Clusters.

    Science.gov (United States)

    Ďorďovič, Vladimír; Tošner, Zdeněk; Uchman, Mariusz; Zhigunov, Alexander; Reza, Mehedi; Ruokolainen, Janne; Pramanik, Goutam; Cígler, Petr; Kalíková, Květa; Gradzielski, Michael; Matějíček, Pavel

    2016-07-01

    This is the first experimental evidence that both self-assembly and surface activity are common features of all water-soluble boron cluster compounds. The solution behavior of anionic polyhedral boranes (sodium decaborate, sodium dodecaborate, and sodium mercaptododecaborate), carboranes (potassium 1-carba-dodecaborate), and metallacarboranes {sodium [cobalt bis(1,2-dicarbollide)]} was extensively studied, and it is evident that all the anionic boron clusters form multimolecular aggregates in water. However, the mechanism of aggregation is dependent on size and polarity. The series of studied clusters spans from a small hydrophilic decaborate-resembling hydrotrope to a bulky hydrophobic cobalt bis(dicarbollide) behaving like a classical surfactant. Despite their pristine structure resembling Platonic solids, the nature of anionic boron cluster compounds is inherently amphiphilic-they are stealth amphiphiles. PMID:27287067

  8. Recent results of boronization on EAST and HT-7 superconducting tokamak

    Energy Technology Data Exchange (ETDEWEB)

    Wu, J.H., E-mail: wujinhua@ipp.ac.cn [Institute of Plasma Physics, P.O. Box 1126, Hefei, Anhui 230031 (China); Hu, J.S., E-mail: hujs@ipp.ac.cn [Institute of Plasma Physics, P.O. Box 1126, Hefei, Anhui 230031 (China); Chen, Y. [Institute of Plasma Physics, P.O. Box 1126, Hefei, Anhui 230031 (China); Ashikawa, N. [National Institute for Fusion Science, Toki, Gifu 509-5292 (Japan); Yu, Y.W.; Li, J.H.; Zuo, G.Z.; Wang, X.M.; Zhao, Y.P.; Li, J.G. [Institute of Plasma Physics, P.O. Box 1126, Hefei, Anhui 230031 (China)

    2011-08-01

    The importance of wall conditionings for the reduction of the impurities in plasmas has been recognized in most tokamaks. Boronization associated with Ion Cyclotron Resonance Frequency discharge (ICRF boronization) has been developed on HT-7 superconducting tokamak since 1998, and now this boronization technique has become a routine method for wall conditioning on HT-7 and also on EAST. Carborane (C{sub 2}B{sub 10}H{sub 12}) was used for the boronization and helium was usually provided as the auxiliary gas. However, after this kind boronization, lots of H{sub 2} released from the boron film make the controlling of the plasma density very difficulty. Recently, to reduce H{sub 2} content in the film, we change the auxiliary gas from He to D{sub 2} during the whole boronization procedure and find the release of H{sub 2} during plasma discharges was greatly reduced.

  9. A novel boron-loaded liquid scintillator for neutron detection

    Energy Technology Data Exchange (ETDEWEB)

    Bentoumi, G.; Dai, X.; Pruszkowski, E.; Li, L.; Sur, B., E-mail: bentoumg@aecl.ca [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada)

    2012-06-15

    A boron-loaded liquid scintillator (LS) has been optimized for neutron detection application in a high gamma field environment. It is composed of the solvent linear alkylbenzene (LAB), a boron containing material, o-carborane (C{sub 2}B{sub 10}H{sub 12}); a fluor, 2,5-diphenyloxazole (PPO); and a wavelength shifter, 1,4-bis[2-methylstyryl] benzene (bis-MSB). Preparation of the liquid scintillator and optimization of its chemical composition are described. The boron-loaded LS has been tested with a neutron beam at the National Research Universal (NRU) reactor. A peak at an equivalent energy of 60 keV is observed in the energy spectrum and is attributed to neutrons. The results confirm the possibility of using B-10 loaded scintillator as a sensitive medium for neutron detection in a relatively large background of gamma rays. (author)

  10. Boron-loaded plastic scintillator with neutron-γ pulse shape discrimination capability

    Energy Technology Data Exchange (ETDEWEB)

    Pawełczak, I.A., E-mail: pawelczak1@llnl.gov; Glenn, A.M.; Martinez, H.P.; Carman, M.L.; Zaitseva, N.P.; Payne, S.A.

    2014-07-01

    Development of the plastic scintillator with neutron sensitivity from thermal to multi-MeV and pulse shape discrimination (PSD) has been demonstrated. Incorporation of {sup 10}B-containing compounds into the plastic scintillator with PSD capability leads to detector improvement in regard to neutron detection efficiency while preserving the discrimination between neutrons and γ-rays. Effects of boron loading on scintillation and pulse shape discrimination properties are discussed. A PSD figure-of-merit value of 1.4±0.03 has been achieved for events in a thermal neutron energy domain, 50–100 keV{sub ee}, for PSD plastic loaded with 5 wt.% of m-carborane.

  11. The local structure of transition metal doped semiconducting boron carbides

    Energy Technology Data Exchange (ETDEWEB)

    Liu Jing; Dowben, P A [Department of Physics and Astronomy and the Nebraska Center for Materials and Nanoscience, Behlen Laboratory of Physics, University of Nebraska-Lincoln, PO Box 880111, Lincoln, NE 68588-0111 (United States); Luo Guangfu; Mei Waining [Department of Physics, University of Nebraska at Omaha, Omaha, NE 68182-0266 (United States); Kizilkaya, Orhan [J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Hwy., Baton Rouge LA 70806 (United States); Shepherd, Eric D; Brand, J I [College of Engineering, and the Nebraska Center for Materials and Nanoscience, N209 Walter Scott Engineering Center, 17th and Vine Streets, University of Nebraska-Lincoln, Lincoln, NE 68588-0511 (United States)

    2010-03-03

    Transition metal doped boron carbides produced by plasma enhanced chemical vapour deposition of orthocarborane (closo-1,2-C{sub 2}B{sub 10}H{sub 12}) and 3d metal metallocenes were investigated by performing K-edge extended x-ray absorption fine structure and x-ray absorption near edge structure measurements. The 3d transition metal atom occupies one of the icosahedral boron or carbon atomic sites within the icosahedral cage. Good agreement was obtained between experiment and models for Mn, Fe and Co doping, based on the model structures of two adjoined vertex sharing carborane cages, each containing a transition metal. The local spin configurations of all the 3d transition metal doped boron carbides, Ti through Cu, are compared using cluster and/or icosahedral chain calculations, where the latter have periodic boundary conditions.

  12. An Unprecedented Formal [5 + 2] Cycloaddition of Nitrones with o-Carboryne via Tandem [3 + 2] Cycloaddition/Oxygen Migration/Aromatization Sequence.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2015-11-01

    Heterocyclic skeletons are widespread among natural products as well as bioactive molecules. Cycloaddition reaction has created new opportunities to access heterocycles of great complexity due to its advantage of multiple bond formation in a single step. Here, we describe an unprecedented formal [5 + 2] cycloaddition of nitrone with o-carboryne to afford carborane-fused seven-membered heterocycles. Experimental and theoretical data suggest that a sequence of [3 + 2] cycloaddition, N-O bond cleavage, oxygen migration and rearomatization is involved in this unprecedented reaction. In this process, the nitrone moieties serve as five-atom coupling partners with both heteroatoms being incorporated into the framework of the final products. This new methodology also offers new insight into the chemistry of nitrones. PMID:26467943

  13. Boron Drug Delivery via Encapsulated Magnetic Nanocomposites: A New Approach for BNCT in Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Yinghuai Zhu

    2010-01-01

    Full Text Available Ortho-carborane cages have been successfully attached to modified magnetic nanoparticles via catalytic azide-alkyne cycloadditions between 1-R-2-butyl-Ortho-C2B10H10(R=Me,3;Ph,4 and propargyl group-enriched magnetic nanoparticles. A loading amount of 9.83 mmol boron atom/g starch-matrixed magnetic nanoparticles has been reached. The resulting nanocomposites have been found to be highly tumor-targeted vehicles under the influence of an external magnetic field (1.14T, yielding a high boron concentration of 51.4 μg/g tumor and ratios of around 10 : 1 tumor to normal tissues.

  14. Bis(μ-nitrato-κ2O:Obis{[1,2-bis(diisopropylphosphanyl-1,2-dicarba-closo-dodecaborane-κ2P,P′]silver(I} dichloromethane disolvate

    Directory of Open Access Journals (Sweden)

    Liguo Yang

    2014-04-01

    Full Text Available The title compound, [Ag2(NO32(C14H38B10P22]·2CH2Cl2, was synthesized by the reaction of 1,2-bis(diisopropylphosphanyl-1,2-dicarba-closo-dodecaborane with AgNO3. The resulting dinuclear molecule has crystallographically imposed inversion symmetry. The diisopropylphosphanyl-closo-carborane ligand is coordinated in a bidentate manner to the AgI atom through the two P atoms. The distorted tetrahedral coordination of the metal is completed by two O atoms of two bridging nitrate anions. The separation between the two AgI atoms is 3.8913 (5 Å. C—H...O hydrogen bonds are observed involving the dichloromethane solvent molecule and the nitrate anion.

  15. Physical understanding of cryogenic implant benefits for electrical junction stability

    Energy Technology Data Exchange (ETDEWEB)

    Adeni Khaja, Fareen; Colombeau, Benjamin; Thanigaivelan, Thirumal; Ramappa, Deepak; Henry, Todd [Applied Materials-Varian Semiconductor Equipment, 35 Dory Road, Gloucester, Massachusetts 01930 (United States)

    2012-03-12

    We investigate the effect of cryogenic temperature implants on electrical junction stability for ultra shallow junction applications for sub-32 nm technology nodes and beyond. A comprehensive study was conducted to gain physical understanding of the impact of cryogenic temperature implants on dopant-defect interactions. Carborane (C{sub 2}B{sub 10}H{sub 12}) molecule, a potential alternative to monomer boron was implanted in carbon preamorphized silicon substrates at cryogenic implant temperatures. Results indicate implants at cryogenic temperatures increase dopant activation with reduced diffusion, resulting in lower sheet resistance for a lower junction depth. Further, this study emphasizes the benefits of co-implants performed at cryogenic temperatures as alternative to traditional preamorphizing implants.

  16. B-Loaded Plastic Scintillator on the Base of Polystyrene

    CERN Document Server

    Brudanin, V B; Nemchenok, I B; Smolnikov, A A

    2000-01-01

    A method to produce polystyrene-based plastic scintillators with boron concentration from 0.38 to 5.0% of boron have been developed. o-Carborane was used as B-containing additive. The results of investigations of the optical, spectral and scintillation characteristics are presented and discussed. It is shown that 5% B-loaded scintillator has a light output as much as 70% relative to the unloaded one. High efficiency for thermal neutron registration achieved for produced samples makes it possible to use such scintillators in complex neutron high sensitive spectrometers. Measured level of radioactive contamination in this scintillation materials is good enough for using the B-loaded scintillators in the proposed large scale neutrino experiments.

  17. Gas chromatography determination of fatty acid alkyl esters (methyl and ethyl in the presence of mono., di- and triglycerides

    Directory of Open Access Journals (Sweden)

    Paulo César Narváez Rincón

    2010-04-01

    Full Text Available Determining fatty acid methyl or ethyl esters, in the presence of mono-, di- and tri glycerides, is very important when studying fatty compounds' methanolysis or ethanolysis, as well as for controlling the quality of petrochemical products. This work presents a useful technique for determining fatty acids methyl or ethyl esters by high temperature gas chromastography in the presence of mono-, di- and triglycerides. Samples were silylated with N, O-bis (trimethylsilyl trifluroacetamide (BSTFA and then passed throught a 12m HT5 column coated with a phenyl-polysiloxane-carborane film. Standard methyl and ethyl palmitate, methyl and ethyl oleate, DL-palmitin, dipalmitin, tripalmitin and triolein solutions were used for calibrating the technique, using tricaprin as internal standard. Retention times and response factors were also determined. The results were employed in following-up palm oil methanolysis and ethanolysis reactions.

  18. Developing nitrosocarborane chemistry.

    Science.gov (United States)

    Powley, Samuel L; Schaefer, Louise; Man, Wing Y; Ellis, David; Rosair, Georgina M; Welch, Alan J

    2016-02-28

    The new nitrosocarboranes [1-NO-2-R-1,2-closo-C2B10H10] [R = CH2Cl (1), CH3OCH2 (2) p-MeC6H4 (3), SiMe3 (4) and SiMe2tBu (5)] and [1-NO-7-Ph-1,7-closo-C2B10H10] (6) were synthesised by reaction of the appropriate lithiocarborane in diethyl ether with NOCl in petroleum ether followed by quenching the reaction with aqueous NaHCO3. These bright-blue compounds were characterised spectroscopically and, in several cases, crystallographically including structural determinations of 2 and 6 using crystals grown in situ on the diffractometer from liquid samples. In all cases the nitroso group bonds to the carborane as a 1e substituent (bent C–N–O sequence) and has little or no influence on , the weighted average 11B chemical shift, relative to that in the parent (monosubstituted) carborane. Mono- and dinitroso derivatives of 1,1′-bis(m-carborane), compounds 7 and 8 respectively, were similarly synthesised but attempts to prepare the mononitroso 1,1′-bis(o-carborane) by the same protocol led only to the hydroxylamine species [1-(1′-1′,2′-closo-C2B10H11)-2-N(H)OH-1,2-closo-C2B10H10] (9); the desired compound [1-(1′-1′,2′-closo-C2B10H11)-2-NO-1,2-closo-C2B10H10] (10) was only realised by switching to a non-aqueous work-up. The involvement of water in effecting the net reduction of the NO function in 10 to N(H)OH in 9 was confirmed by a series of experiments involving [1-N(H)OH-2-Ph-1,2-closo-C2B10H10] (11), [1-(1′-2′-D-1′,2′-closo-C2B10H10)-2-D-1,2-closo-C2B10H10] (12) and [1-(1′-2′-D-1′,2′-closo-C2B10H10)-2-N(H)OH-1,2-closo-C2B10H10] (13). It is suggested that during aqueous work-up a water molecule, H-bonded to the acidic C2′H of 10, is "delivered" to the adjacent C2NO unit. The ability of the NO group in nitrosocarboranes to undergo Diels-Alder cycloaddition reactions with cyclic 1,3-dienes was established via the syntheses of [1-(NOC10H14)-1,2-closo-C2B10H11] (14) and [1-(NOC6H8)-2-Ph-1,2-closo-C2B10H10] (15). This strategy was then

  19. For boron neutron capture therapy,synthesizing boron-polymer compounds and testing in laboratory conditions

    International Nuclear Information System (INIS)

    grafted by PEG and Poli(Ac)-g1-2-AEPB-g2-PEG macro branched polymer was synthesized. - Poly(ethylene-alt-maleic anhyride)-PEG-2AEPB was synthesized by esterication of PEG and amidification of 2-AEPB. - Firstly, Poly(ethylene-alt-maleic anhydride) was hydrolized to form water-solube Poly(ethylene-alt-maleic acid). Then, at different mole ratio, 2-AEPB compound was bound to this water soluble polymer. Finally, Poly(ethylene-alt-maleic anhydride)-2-AEPB-PEG was synthesized by esterification of Poly(ethylene-alt-maleic anhydride)-2-AEPB and PEG. Characterization of these macro complex polymers were performed by FTIR, DSC, TGA and NMR analysis. Functional groups which have tumor targeting property will be determined and related experiments will be started. In order to start the cell culture experiments, the required coordination will be done. The second study has been carried out with METU and Adnan Menderes University. Experimental studies have been done in Polymer Chemistry Laboratory and Organic Chemistry Laboratory of Adnan Menderes University. In this study, polyester dendrimer structure was synthesized and characterized by FTIR and NMR analysis. Carborane compound purchased from foreign chemical firm. In order to incorporate polyester dendrimer by carborane, carborane will be functioned by organic synthesis. This study has been carried out in Laboratory of Adnan Menderes University. In this technical report, the first experimental study carried out together with Hacettepe University of boron chemistry group will be discussed.

  20. 半夹芯16电子化合物CpCo(S2C2B10H10)与乙炔基二茂铁在甲醇中的反应性%Reactivity of the Half-Sandwich 16e Compound CpCo(S2C2B10H10) with Ethynylferrocene in Methanol

    Institute of Scientific and Technical Information of China (English)

    叶红德; 白文娟; 郑大贵; 胡久荣; 彭化南; 燕红

    2012-01-01

    The half-sandwich 16e cobalt compound CpCo(S2C2B10H10) (1) (Cp: cyclopentadienyl) reacted with excess ethynylferrocene (FcC = CH) (Fc: ferrocenyl) in methanol to give complex 8 and two ethynylferrocene cyclotrimerization compounds: 1,2,4-triferrocenylbenzene and 1,3,5-triferrocenylbenzene. In 8, two ethynylferrocene molecules are coupled in the head-to-head way and linked to the two sulfur atoms of the CpCo (S2C2B10H10) molecule, leading to loss of the CpCo unit. The BH bond at B(3) site of the carborane cage has been activated and the boron atom was connected to the terminal carbon of one alkyne to generate a C-B bond. Whereas the BH apex at the B(6) site has been lost in the presence of methanol, as a result, the closo-C2B10 carborane cage was converted into a nido-C2B9 carborane cage. The complex 8 has been characterized by single-crystal X-ray diffraction analysis. CCDC: 808991.%半夹芯16电子化合物CpCo(S2C2B10H10) (1)(Cp:cyclopentadienyl)与过量乙炔基二茂铁(FcC≡CH)(Fc:ferrocenyl)在甲醇中反应,分离得到了化合物(CHCFc)(CH=CFc)(S2C2B9H10)(8)和2个乙炔基二茂铁环三聚产物1,2,4-三二茂铁基苯和1,3,5-三二茂铁基苯.在8中,2个乙炔基二茂铁分子以“头对头”方式聚合连接到CpCo(S2C2B10H10)分子中的2个S原子上,导致CpCo结构单元的丢失.碳硼烷笼体B(3)位上的BH键发生活化,该B原子与1个乙炔基二茂铁分子的乙炔基末端C原子连接生成C-B键;同时,B(6)位的BH碎片在甲醇作用下失去,从而closo-C2B10闭式结构转变成nido-C2B9巢式结构.化合物8用单晶X-射线衍射分析方法进行了表征.

  1. Boron-Containing Compounds for Liposome-Mediated Tumor Localization and Application to Neutron Capture Therapy

    International Nuclear Information System (INIS)

    unimolecular nanoparticles presenting several advantages: tunable size through functionalization and branching, spherical shape due to the icosahedral B122 core, promising water solubility resulting from degradation of all pendant closo-carborane groups to their hydrophilic nido anion substituents, and efficient boron delivery owing to the presence of 120 boron atoms which gives rise to a boron content as high as 40% by weight. Keeping the new objective in mind, we have focused on the design, synthesis and evaluation of new and very boron-rich closomer species. Additionally, progress has also been made toward the evaluation of a newly synthesized boron-rich lipid as a substitute for DSPC in bilayer construction, and the boron content of the resulting liposomes has been greatly enhanced. Related research involving the synthesis and self-assembly of carborane-containing amphiphiles has been systematically studied. Combined hydrophobic and hydrophilic properties of the single-chain amphiphiles allow their spontaneous self-assembly to form rods under a variety of variable conditions, such as concentration in the bilayer, carborane cage structure, chain-length, counterion identity, solvents, methods of preparation, and the ionic charge. On the other hand, the number of attached chains affects the self-assembly process. Particles having totally different shapes have been observed for dual-chain amphiphiles.

  2. Boron-Containing Compounds for Liposome-Mediated Tumor Localization and Application to Neutron Capture Therapy

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick [Univ. of California, Los Angeles, CA (United States)

    2005-04-07

    amphiphilic unimolecular nanoparticles presenting several advantages: tunable size through functionalization and branching, spherical shape due to the icosahedral B122 core, promising water solubility resulting from degradation of all pendant closo-carborane groups to their hydrophilic nido anion substituents, and efficient boron delivery owing to the presence of 120 boron atoms which gives rise to a boron content as high as 40% by weight. Keeping the new objective in mind, we have focused on the design, synthesis and evaluation of new and very boron-rich closomer species. Additionally, progress has also been made toward the evaluation of a newly synthesized boron-rich lipid as a substitute for DSPC in bilayer construction, and the boron content of the resulting liposomes has been greatly enhanced. Related research involving the synthesis and self-assembly of carborane-containing amphiphiles has been systematically studied. Combined hydrophobic and hydrophilic properties of the single-chain amphiphiles allow their spontaneous self-assembly to form rods under a variety of variable conditions, such as concentration in the bilayer, carborane cage structure, chain-length, counterion identity, solvents, methods of preparation, and the ionic charge. On the other hand, the number of attached chains affects the self-assembly process. Particles having totally different shapes have been observed for dual-chain amphiphiles.

  3. Synthesis and evaluation of boron folates for Boron-Neutron-Capture-Therapy (BNCT)

    Energy Technology Data Exchange (ETDEWEB)

    Kettenbach, Kathrin; Schieferstein, Hanno; Grunewald, Catrin; Hampel, Gabriele; Schuetz, Christian L. [Mainz Univ. (Germany). Inst. of Nuclear Chemistry; Iffland, Dorothee; Bings, Nicolas H. [Mainz Univ. (Germany). Inst. of Inorganic Chemistry and Analytical Chemistry; Reffert, Laura M. [Hannover Medical School (Germany). Radiopharmaceutical Chemistry; Ross, Tobias L. [Mainz Univ. (Germany). Inst. of Nuclear Chemistry; Hannover Medical School (Germany). Radiopharmaceutical Chemistry

    2015-07-01

    Boron neutron capture therapy (BNCT) employs {sup 10}B-pharmaceuticals administered for the treatment of malignancies, and subsequently irradiated with thermal neutrons. So far, clinical established pharmaceuticals like boron phenylalanine (BPA) or sodium boron mercaptate (BSH) use imperfect (BPA) or passive (BSH) targeting for accumulation at target sites. Due to the need of a selective transportation of boron drugs into cancer cells and sparing healthy tissues, we combined the BNCT approach with the specific and effective folate receptor (FR) targeting concept. The FR is overexpressed on many human carcinomas and provides a selective and specific target for molecular imaging as well as for tumor therapy. We synthesized and characterized a carborane-folate as well as a BSH-folate to study their in vitro characteristics and their potential as new boron-carriers for BNCT. Uptake studies were carried out using human KB cells showing a significant increase of the boron content in cells and demonstrating the successful combination of active FR-targeting and BNCT.

  4. Initial phase wall conditioning in KSTAR

    International Nuclear Information System (INIS)

    The initial phase wall conditioning in KSTAR is depicted. The KSTAR wall conditioning procedure consists of vessel baking, glow discharge cleaning (GDC), ICRH wall conditioning (ICWC) and boronization (Bz). Vessel baking is performed for the initial vacuum conditioning in order to remove various kinds of impurities including H2O, carbon and oxygen and for the plasma operation. The total outgassing rates after vessel baking in three successive KSTAR campaigns are compared. GDC is regularly performed as a standard wall cleaning procedure. Another cleaning technique is ICWC, which is useful for inter-shot wall conditioning under a strong magnetic field. In order to optimize the operation time and removal efficiency of ICWC, a parameter scan is performed. Bz is a standard technique to remove oxygen impurity from a vacuum vessel. KSTAR has used carborane powder which is a non-toxic boron-containing material. The KSTAR Bz has been successfully performed through two campaigns: water and oxygen levels in the vacuum vessel are reduced significantly. As a result, KSTAR has achieved its first L-H mode transition, although the input power was marginal for the L-H transition threshold. The characteristics of boron-containing thin films deposited for boronization are investigated.

  5. CARBON NANOTUBES: AN APPROACH TO NOVEL DRUG DELIVERY SYSTEM

    Directory of Open Access Journals (Sweden)

    M. H. Alai et al.

    2012-01-01

    Full Text Available Carbon nanotubes are cylindrical carbon molecules have novel properties, making them potentially useful in many applications in nanotechnology, electronics, optics, and other fields of material science as well as potential uses in architectural fields. They have unique electronic, mechanical, optical and chemical properties that make them good candidates for a wide variety of applications, including drug transporters, new therapeutics, delivery systems and diagnostics. Their unique surface area, stiffness, strength and resilience have led to much excitement in the field of pharmacy. Nanotubes are categorized as single-walled nanotubes, multiple walled nanotubes. Various techniques have been developed to produce nanotubes in sizeable quantities, including arc discharge, laser ablation, chemical vapor deposition. They can pass through membranes, carrying therapeutic drugs, vaccines and nucleic acids deep into the cell to targets previously unreachable. Purification of the tubes can be divided into a couple of main techniques: oxidation, acid treatment, annealing, sonication, filtering and functionalization techniques. The main problem of insolubility in aqueous media has been solved by developing a synthetic protocol that allows highly water-soluble carbon NTs to be obtained. The modifications are done to improve efficiency of carbon nanotubes by formulating luminescent carbon nanotubes, ultrathin carbon nanoneedles, magnetically guided nanotubes. The application of carbon nanotube in tissue engineering, drug carrier release system, wound healing, in cancer treatment and as biosensor. Researchers have recently developed a new approach to Boron Neutron Capture Therapy in the treatment of cancer using substituted Carborane-Appended Water-Soluble single-wall carbon nanotubes.

  6. Multidimensional potential of boron-containing molecules in functional materials

    Indian Academy of Sciences (India)

    Wolfgang Kaim; Narayan S Hosmane

    2010-01-01

    Boron-containing molecular systems have received much attention under theoretical aspects and from the side of synthetic organic chemistry. However, their potential for further applications such as optically interesting effects such as Non-Linear Optics (NLO), medical uses for Boron Neutron Capture Therapy (BNCT), or magnetism has been recognised only fairly recently. Molecular systems containing boron offer particular mechanisms to accommodate unpaired electrons which may result in stable radicals as spin-bearing materials. Among such materials are organoboron compounds in which the prototypical electron deficient (10B, 11B) boron vs. carbon centers can accept and help to delocalise added electrons in a 2-dimensionally conjugated system. Alternatively, oligoboron clusters B$_{n}$X$_{n}^{k}$ and the related carboranes or metallacarboranes are capable of adding or losing single electrons to form paramagnetic clusters with 3-dimensionally delocalised spin, according to combined experimental studies and quantum chemical calculations. The unique nuclear properties of 10B are of therapeutic value if their selective transport via appended carbon nanotubes, boron nanotubes, or magnetic nanoparticles can be effected.

  7. Proceedings of workshop on 'boron chemistry and boron neutron capture therapy'

    International Nuclear Information System (INIS)

    This volume contains the proceedings of the 4th Workshop on 'the Boron Chemistry and Boron Neutron Capture Therapy' held on February 24 in 1992. First, clinical experiences of BNCT in the Kyoto University Research Reactor in 1992 were briefly reported. Then, the killing effects of boron cluster-containing nucleic acid precursors on tumor cells were shown (Chap. 2). The various trials of the optical resolution of B-p-boronophenylalanine for neutron capture therapy were made (Chap. 3). The borate-dextran gel complexes were investigated by the nuclear magnetic resonance spectroscopy. The stability constants of borate complexes were listed, and are useful in the solution chemistry of boron compounds (Chap. 4). The interactions between boron compounds and biological materials were studied by the paper electrophoresis which had been developed by us (Chap. 5). Molecular design of boron-10 carriers and their organic synthesis were reported (Chap. 6). Carborane-containing aziridine boron carriers which were directed to the DNA alkylation were synthesized and their cancer cell killing efficacies were tested (Chap. 7). The solution chemistry of deuterium oxide which is a good neutron moderator was reported, relating to the BNCT (Chap. 8). (author)

  8. Analysis of boron carbides' electronic structure

    Science.gov (United States)

    Howard, Iris A.; Beckel, Charles L.

    1986-01-01

    The electronic properties of boron-rich icosahedral clusters were studied as a means of understanding the electronic structure of the icosahedral borides such as boron carbide. A lower bound was estimated on bipolaron formation energies in B12 and B11C icosahedra, and the associated distortions. While the magnitude of the distortion associated with bipolaron formation is similar in both cases, the calculated formation energies differ greatly, formation being much more favorable on B11C icosahedra. The stable positions of a divalent atom relative to an icosahedral borane was also investigated, with the result that a stable energy minimum was found when the atom is at the center of the borane, internal to the B12 cage. If incorporation of dopant atoms into B12 cages in icosahedral boride solids is feasible, novel materials might result. In addition, the normal modes of a B12H12 cluster, of the C2B10 cage in para-carborane, and of a B12 icosahedron of reduced (D sub 3d) symmetry, such as is found in the icosahedral borides, were calculated. The nature of these vibrational modes will be important in determining, for instance, the character of the electron-lattice coupling in the borides, and in analyzing the lattice contribution to the thermal conductivity.

  9. The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy.

    Science.gov (United States)

    Paquette, Michelle M; Li, Wenjing; Sky Driver, M; Karki, Sudarshan; Caruso, A N; Oyler, Nathan A

    2011-11-01

    Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases. PMID:21959982

  10. The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy

    International Nuclear Information System (INIS)

    Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (BxC:Hy) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the BxC:Hy intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases. (paper)

  11. Antibodies and antiestrogens combined with boron for use in the neutron capture therapy

    International Nuclear Information System (INIS)

    The ZR-75-1 cell line developed from a mammary carcinoma was chosen to characterise the binding of antiestrogen U23.469-M to the cell, which was subsequently compared to that of a derivative combined with boron. It was found that the original U23.469-M showed antiestrogenic activity, while this effect was largely abolished after the substance had been modified using b-decachloro-o-carborane. In this study, boron-conjugated antibodies were produced in order to find out whether those modified immunoglobulins would be suitable to bind sufficient quantities of boron to the tumour cells. It was calculated by experts on radiation biology that a minimum of 1000 boron atoms is required for a tumour-specific antibody to be therapeutically effective. When oxidated dextran of a molecular weight of 33 kD was used as a linking molecule, a reproducible method could be developed that permitted more than 1000 boron atoms to be bound per antibody. In one of the monoclonal antibodies tested here a combination with boron could, however, only be achieved at the expense of complete inactivation. A model was developed allowing to significantly increase the number modified antibodies attached to any one tumour cell. The cell binding experiments and radioimmunoassays then carried out were able to show that the number of antibodies bound to tumour cells can be increased to different degrees, depending on the monoclonal antibody used in each case. (orig./MG)

  12. On the management of radioactive wastes and the concept of HAW partitioning

    International Nuclear Information System (INIS)

    The report presents information on arising of radioactive wastes in the Community countries and organizations responsible for waste storage, reprocessing and disposal. Data are given on amounts of different wastes accumulated so far and stored in liquid and solid state, as well as in the form of vitrified blocks. Main legislative documents regulating the waste management, as well as information on scientific organizations responsible for the development of methods for radioactive waste management are considered. Alternative methods for management of long-lived technogeneous radionuclides, which are now under development when realizing the closed fuel cycle, are discussed including disposal into geological formations, transmutation and removal into space. Principal approaches to performing each of the methods mentioned above are reviewed. Concept of HAW partitioning with recovery of TUE and long-lived fission products into individual fractions is described. A review of developments is presented concerning the extraction methods with carboranes, crown ethers and bidentate extractants, as well as the sorption methods with the use of ferrocyanide materials and ampholytes. (author)

  13. NMR of dielectrically oriented molecules

    International Nuclear Information System (INIS)

    General information on experimental aspects of EFNMR is given. It is shown that the complete 14N quadrupole tensor (qct) of pyridine and pyrimidine in the liquid state is accessible to EFNMR. Information obtained about 17O qct in liquid nitromethane, is compared with results from other techniques. The 33S qct in liquid sulfolane is investigated. The EFNMR results, combined with those from spin-lattice relaxation time measurements and from Hartree-Fock-Slater MO calculations, allowed the complete assignment of the 33S qct. The quadrupole coupling of both 10B and 11B in a carborane compound is investigated and, together with the results of spin-lattice relaxation time measurements, detailed information about the assignment of the boron qct's could be derived. EFNMR studies of apolar molecules are described. A limitation in EFNMR is the inhomogeneity (delta B) of the magnetic field, which is introduced by the use of non-spinning sample cells. A way out is the detection of zero quantum transitions, their widths being independent of delta B. The results and prospectives of this approach are shown for the simple three spin 1/2 system of acrylonitrile in which the small dipolar proton-proton couplings could be revealed via zero quantum transitions. (Auth.)

  14. Development of boronated tumor-seeking materials for application in neutron capture therapy of cancer

    International Nuclear Information System (INIS)

    Full text: At the present time the main field of application of boron compounds in medicine is Boron Neutron Capture Therapy (BNCT) of cancer. In this presentation the main principles of BNCT and main types of polyhedral boron compounds used for BNCT will be shown. The successful treatment of tumors by BNCT requires selective delivery of the boron moiety into the tumor cells. One of ways to solve this problem is attachment of boron fragment to different tumor-specific targeting molecules. Literature and our recent results on the preparation of novel boronated amino acids, carboranecarboxylic acids, a design of different conjugates of polyhedral boron compounds with tumor-seeking molecules, like porphyrins, phthalocyanines, nucleosides, carbohydrates, and lipids will be presented. Conjugates of natural porphyrins and phthalocyanines with carborane, closo-dodecaborate and cobalt bis(dicarbollide) were synthesized. The combination of these two fragments in one molecule makes these compounds potentially useful for both fluorescence diagnostics (FD) and BNCT of tumours. Boronated nucleosides are considered to be potential BNCT candidates because they can accumulate in the tumor cells. Thus, we have succeeded in preparation of the very first conjugates of closo-dodecaborate anion with one canonic nucleoside (thymidine)

  15. Synthesis of triazolyl methyl-substituted amino- and oxy-undeca-hydro-dodeca-borates for potential application in boron neutron capture therapy

    International Nuclear Information System (INIS)

    A general approach to the synthesis of triazole conjugates containing undeca-hydro-closo-dodeca-borate anions based on Huisgen 1, 3-dipolar cycloaddition is presented. Un-decahydro-closo-dodeca-borate anions bearing terminal alkyne groups were synthesized by the reaction of H3N-B12H11- or HO-B12H112- with alkyne halides in N, N-dimethylformamide using KOH as a base. Variation of reaction time, alkyne halide concentration and steric demands of the alkyne halide resulted in the stepwise introduction of one to three alkyne groups into H3N-B12H11-. Two compounds {(CHCCH2)-N-B12H11- and (CHCCH2)O-B12H112-} were crystallized for single-crystal X-ray diffraction studies. N- and O-alkyne un-decahydro-closo-dodeca-borate anions reacted with various functionalized azides including lipid, carborane, aryl and hydroxyalkyl groups. The current study provides various synthetic applications not only for BNCT but also for boron cluster materials. (authors)

  16. Application of the boron neutron capture therapy to undifferentiated thyroid cancer using two boron compounds (BPA and BOPP)

    International Nuclear Information System (INIS)

    We have shown the selective uptake of boronophenylalanine (BPA) by undifferentiated thyroid cancer (UTC) human cell line ARO, both in vitro and in vivo. Moreover, a 50% histologic cure of mice bearing the tumor was observed when the complete boron neutron capture therapy was applied. More recently we have analyzed the biodistribution of BOPP (tetrakis-carborane carboxylate ester of 2,4-bis-(ba-dihydroxyethyl)-deutero-porphyrin IX) and showed that when BOPP was injected 5 days before BPA, and the animals were sacrificed 60 min after the ip injection of BPA, a significant increase in boron uptake by the tumor was found (38-45ppm with both compounds Vs. 20 ppm with BPA alone). Five days post the ip BOPP injection and 1 hr after BPA, the ratios were: tumor/blood 3,75; tumor /distal skin 2. Other important ratios were tumor/thyroid 6,65 and tumor/lung 3,8. The present studies were performed in mice transplanted with ARO cells and injected with BOPP and BPA. Only in mice treated with the neutron beam and injected with the boronated compounds we observed a 100% control of tumor growth. Two groups of mice received different total absorbed doses: 3.00 and 6.01 Gy, but no further improvement in the outcome was found compared to the previous results using BPA alone (4.3 Gy). (author)

  17. Characterization of designed cobaltacarborane porphyrins using conductive probe atomic force microscopy

    Directory of Open Access Journals (Sweden)

    Venetia D. Lyles

    2016-03-01

    Full Text Available Porphyrins and metalloporphyrins have unique chemical and electronic properties and thus provide useful model structures for studies of nanoscale electronic properties. The rigid planar structures and -conjugated backbones of porphyrins convey robust electrical characteristics. For our investigations, cobaltacarborane porphyrins were synthesized using a ring-opening zwitterionic reaction to produce isomers with selected arrangements of carborane clusters on each macrocycle. Experiments were designed to investigate how the molecular structure influences the self-organization, surface assembly, and conductive properties of three molecular structures with 2, 4, or 8 cobaltacarborane substituents. Current versus voltage (I-V spectra for designed cobaltacarborane porphyrins deposited on conductive gold substrates were acquired using conductive probe atomic force microscopy (CP-AFM. Characterizations with CP-AFM provide capabilities for obtaining physical measurements and structural information with unprecedented sensitivity. We found that the morphology of cobaltacarborane porphyrin structures formed on surfaces depends on a complex interplay of factors such as the solvent used for dissolution, the nature of the substrate, and the design of the parent molecule. The conductive properties of cobaltacarborane porphyrins were observed to change according to the arrangement of cobaltacarborane substituents. Specifically, the number and placement of the cobaltacarborane ligands on the porphyrin macrocycle affect the interactions that drive porphyrin self-assembly and crystallization. Interestingly, coulombic staircase I-V profiles were detected for a porphyrin with two cobaltacarborane substituents.

  18. Carboranyl-Chlorin e6 as a Potent Antimicrobial Photosensitizer.

    Directory of Open Access Journals (Sweden)

    Elena O Omarova

    Full Text Available Antimicrobial photodynamic inactivation is currently being widely considered as alternative to antibiotic chemotherapy of infective diseases, attracting much attention to design of novel effective photosensitizers. Carboranyl-chlorin-e6 (the conjugate of chlorin e6 with carborane, applied here for the first time for antimicrobial photodynamic inactivation, appeared to be much stronger than chlorin e6 against Gram-positive bacteria, such as Bacillus subtilis, Staphyllococcus aureus and Mycobacterium sp. Confocal fluorescence spectroscopy and membrane leakage experiments indicated that bacteria cell death upon photodynamic treatment with carboranyl-chlorin-e6 is caused by loss of cell membrane integrity. The enhanced photobactericidal activity was attributed to the increased accumulation of the conjugate by bacterial cells, as evaluated both by centrifugation and fluorescence correlation spectroscopy. Gram-negative bacteria were rather resistant to antimicrobial photodynamic inactivation mediated by carboranyl-chlorin-e6. Unlike chlorin e6, the conjugate showed higher (compared to the wild-type strain dark toxicity with Escherichia coli ΔtolC mutant, deficient in TolC-requiring multidrug efflux transporters.

  19. Tetraethylammonium 7,12-dicyano-1-carba-closo-dodecaborate

    Directory of Open Access Journals (Sweden)

    Marcus A. Juhasz

    2014-04-01

    Full Text Available In the title compound, C8H20N+·C3H10B11N2−, the carborane anion cage displays nearly-perfect Cs symmetry, with the two CN groups lying on a noncrystallographic mirror plane that bisects the cage. In the crystal, the anions form extended chains along the a-axis direction, with C—H...N hydrogen bonds linking consecutive anions. The C[triple-bond]N bond lengths (and B—C[triple-bond]N angles in the nitrile moities are 1.1201 (19 Å, 178.60 (15° and 1.1433 (17 Å, 179.45 (15°, similar to those observed in organic nitriles. A hydrogen bond between a methylene H atom of the cation and the N atom in one of the nitrile groups of the anion is the closest contact between the anion and cation, at 2.52 Å.

  20. Second-order nonlinear optical responses of carboranyl-substituted indole/indoline derivatives: impact of different substituents.

    Science.gov (United States)

    Wang, Hong-Qiang; Wang, Wen-Yong; Fang, Xin-Yan; Wang, Li; Zhu, Chang-Li; Chen, Zhen-Zhen; Chen, He; Qiu, Yong-Qing

    2016-06-01

    Carborane has been the subject of great interest over the last decades due to its high structural, chemical, biological stability and diverse applications. In the present work, carboranyl-substituted indole/indoline compounds and their functionalized derivatives have been systematically investigated by density functional theory (DFT) method with the view of assessing their electronic structures and first hyperpolarizabilities. Significantly, the first hyperpolarizabilities can be obviously enhanced by the introduction of a strong electron-withdrawing group for closed-ring forms, while the strong electron-donating group is beneficial for large first hyperpolarizabilities for open-ring forms. It indicates that the NLO properties of these compounds can be enhanced by controlling their relative substituent groups. Furthermore, the time-dependent DFT calculation illustrates that the enhancement of the first hyperpolarizabilities are found due to the obvious charge transfer (CT) transition, and closed-ring forms have a significant difference on the CT patterns versus open-ring ones. Investigation of the structure-property relationship and substituent effects at the molecular level can benefit for further exploration of carboranyl-substituted indole/indoline derivatives with versatile and fascinating NLO properties. PMID:27262529

  1. Epitaxial B-Graphene: Large-Scale Growth and Atomic Structure.

    Science.gov (United States)

    Usachov, Dmitry Yu; Fedorov, Alexander V; Petukhov, Anatoly E; Vilkov, Oleg Yu; Rybkin, Artem G; Otrokov, Mikhail M; Arnau, Andrés; Chulkov, Evgueni V; Yashina, Lada V; Farjam, Mani; Adamchuk, Vera K; Senkovskiy, Boris V; Laubschat, Clemens; Vyalikh, Denis V

    2015-07-28

    Embedding foreign atoms or molecules in graphene has become the key approach in its functionalization and is intensively used for tuning its structural and electronic properties. Here, we present an efficient method based on chemical vapor deposition for large scale growth of boron-doped graphene (B-graphene) on Ni(111) and Co(0001) substrates using carborane molecules as the precursor. It is shown that up to 19 at. % of boron can be embedded in the graphene matrix and that a planar C-B sp(2) network is formed. It is resistant to air exposure and widely retains the electronic structure of graphene on metals. The large-scale and local structure of this material has been explored depending on boron content and substrate. By resolving individual impurities with scanning tunneling microscopy we have demonstrated the possibility for preferential substitution of carbon with boron in one of the graphene sublattices (unbalanced sublattice doping) at low doping level on the Ni(111) substrate. At high boron content the honeycomb lattice of B-graphene is strongly distorted, and therefore, it demonstrates no unballanced sublattice doping. PMID:26121999

  2. The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Paquette, Michelle M; Sky Driver, M; Karki, Sudarshan; Caruso, A N [Department of Physics, University of Missouri-Kansas City, Kansas City, MO 64110 (United States); Li Wenjing; Oyler, Nathan A, E-mail: oylern@umkc.edu [Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 (United States)

    2011-11-02

    Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B{sub x}C:H{sub y}) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B{sub x}C:H{sub y} intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, {approx}40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases. (paper)

  3. Molecules with ''wheels'' on a metal surface

    Energy Technology Data Exchange (ETDEWEB)

    Villagomez, Carlos; Grill, Leonhard [Institut fuer Experimentalphysik, Freie Universitaet Berlin (Germany); Sasaki, Takashi; Tour, James M. [Chemistry Department, Rice University, Houston, TX (United States)

    2009-07-01

    The design and creation of molecular nanostructures with specific mechanical functions is one of the fundamental issues in nanotechnology. In this context, wheels are an interesting component for the molecular motion, because they are expected to alter the diffusion properties on surfaces, for instance by allowing only directed motion. In the presented work, we show the absorption of functional molecules studied by scanning tunneling microscopy under ultrahigh vacuum at low temperatures of about 7 K. The molecules consist of a phenyl chain, equipped with carborane side groups that represent the molecular ''wheels''. Additionally, bromine atoms are attached to the terminal groups of the molecules, which should allow the covalent connection of individual molecules, according to our recently presented oen-surface-synthesis'' method. The high mobility of the molecules during deposition, at room temperature, enables them to form molecular nanostructures. Characteristic appearances of the molecules, due to different molecular configurations, are found. Furthermore, lateral manipulation was used to displace molecules and to probe their intermolecular interactions.

  4. Synthesis and evaluation of thymidine kinase 1-targeting carboranyl pyrimidine nucleoside analogs for boron neutron capture therapy of cancer.

    Science.gov (United States)

    Agarwal, Hitesh K; Khalil, Ahmed; Ishita, Keisuke; Yang, Weilian; Nakkula, Robin J; Wu, Lai-Chu; Ali, Tehane; Tiwari, Rohit; Byun, Youngjoo; Barth, Rolf F; Tjarks, Werner

    2015-07-15

    A library of sixteen 2nd generation amino- and amido-substituted carboranyl pyrimidine nucleoside analogs, designed as substrates and inhibitors of thymidine kinase 1 (TK1) for potential use in boron neutron capture therapy (BNCT) of cancer, was synthesized and evaluated in enzyme kinetic-, enzyme inhibition-, metabolomic-, and biodistribution studies. One of these 2nd generation carboranyl pyrimidine nucleoside analogs (YB18A [3]), having an amino group directly attached to a meta-carborane cage tethered via ethylene spacer to the 3-position of thymidine, was approximately 3-4 times superior as a substrate and inhibitor of hTK1 than N5-2OH (2), a 1st generation carboranyl pyrimidine nucleoside analog. Both 2 and 3 appeared to be 5'-monophosphorylated in TK1(+) RG2 cells, both in vitro and in vivo. Biodistribution studies in rats bearing intracerebral RG2 glioma resulted in selective tumor uptake of 3 with an intratumoral concentration that was approximately 4 times higher than that of 2. The obtained results significantly advance the understanding of the binding interactions between TK1 and carboranyl pyrimidine nucleoside analogs and will profoundly impact future design strategies for these agents. PMID:26087030

  5. The salts of chloronium ions R-Cl(+)-R (R = CH3 or CH2Cl): formation, thermal stability, and interaction with chloromethanes.

    Science.gov (United States)

    Stoyanov, Evgenii S

    2016-05-14

    The interaction of CH3Cl/CD3Cl or CH2Cl2/CD2Cl2 with the carborane acid H(CHB11Cl11) (abbreviated as H{Cl11}) generates the salts of CH3-{Cl11} and CH2Cl-{Cl11} and their deuterio analogs, respectively, which are analogs of the salts of asymmetric chloronium cations. Next, salts of chloronium cations CH3-Cl(+)-CH3, ClCH2-Cl(+)-CH2Cl, and ClCH2-Cl(+)-CH3 and their deuterio analogs were obtained from the above compounds. The asymmetric ClCH2-Cl(+)-CH3 cation was found to be unstable, and at ambient temperature, slowly disproportionated into symmetric cations (CH3)2Cl(+) and (CH2Cl)2Cl(+). At a high temperature (150 °C), disproportionation was completed within 5 minutes, and the resulting cations further decomposed into CH3-{Cl11} and CH2Cl-{Cl11}. The molecular fragment ClCH2-(X) of the compounds (X = {Cl11}, -Cl(+)-CH2Cl, or -Cl(+)-CH3) is involved in exchange reactions with CH2Cl2 and CHCl3, converting into CH3-(X) with the formation of chloroform and CCl4, respectively. PMID:27104946

  6. Surface analysis of VPS-W coatings boronized by an ICRF discharge in HT-7

    Energy Technology Data Exchange (ETDEWEB)

    Yang Zhongshi, E-mail: zsyang@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, PO. Box 1126, Hefei 230031 (China); Wang Wanjing [Institute of Plasma Physics, Chinese Academy of Sciences, PO. Box 1126, Hefei 230031 (China); Radiosicence Research Laboratory, Shizuoka University, 836 Oya, Shizuoka 422-8529 (Japan); Li Qiang; Wu Jing [Institute of Plasma Physics, Chinese Academy of Sciences, PO. Box 1126, Hefei 230031 (China); Okuno, Kenji; Oya, Yasuhisa [Radiosicence Research Laboratory, Shizuoka University, 836 Oya, Shizuoka 422-8529 (Japan); Luo Guangnan, E-mail: gnluo@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, PO. Box 1126, Hefei 230031 (China)

    2011-10-01

    To understand the surface compositions and the hydrogen isotope behavior in boronized Vacuum plasma spraying (VPS)-W, the boron coating has been achieved by means of Ion Cyclotron Radio Frequency (ICRF) boronization using carborane (C{sub 2}B{sub 10}H{sub 12}) powder as the precursor material in HT-7. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) were used to observe the morphology of the VPS-W and boronized W surfaces. The X-ray Photoelectron Spectroscopy (XPS) of W-4f, O-1s, C-1s and B-1s on the VPS-W sample before and after boronization and after plasma exposure have been measured. The B-B and B-C bonds were observed after boronization treatment for VPS-W. Thermal Desorption Spectroscopy (TDS) experiments were also carried out to investigate the thermal desorption behavior of D implanted into the samples. After HT-7 plasma exposure, the desorption spectrum had a low temperature peak associated with trapping in intrinsic defects in polycrystalline W and a high temperature peak associated with B-O-D and B-C-D bonds.

  7. Sources and transport systems for low energy extreme of ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Hershcovitch, A.; Batalin, V.A.; Bugaev, A.S.; Gushenets, V.I.; Alexeyenko, O.; Gurkova, E.; Johnson, B.M.; Kolomiets, A.A.; Kropachev, G.N.; Kuibeda, R.P.; Kulevoy, T.V.; Masunov, E.S.; Oks, E.M.; Pershin, V.I.; Polozov, S.M.; Poole, H.J.; Seleznev, D.N.; Storozhenko, P.A.; Vizir, A.; Svarovski, A.Ya.; Yakushin, P.; Yushkov, G.Yu.

    2010-06-06

    For the past seven years a joint research and development effort focusing on the design of steady state, intense ion sources has been in progress with the ultimate goal being to meet the two, energy extreme range needs of mega-electron-volt and 100's of electron-volt ion implanters. However, since the last Fortier is low energy ion implantation, focus of the endeavor has shifted to low energy ion implantation. For boron cluster source development, we started with molecular ions of decaborane (B{sub 10}H{sub 14}), octadecaborane (B{sub 18}H{sub 22}), and presently our focus is on carborane (C{sub 2}B{sub 10}H{sub 12}) ions developing methods for mitigating graphite deposition. Simultaneously, we are developing a pure boron ion source (without a working gas) that can form the basis for a novel, more efficient, plasma immersion source. Our Calutron-Berna ion source was converted into a universal source capable of switching between generating molecular phosphorous P{sub 4}{sup +}, high charge state ions, as well as other types of ions. Additionally, we have developed transport systems capable of transporting a very large variety of ion species, and simulations of a novel gasless/plasmaless ion beam deceleration method were also performed.

  8. Bonding in transition-metal cluster compounds. 2. The metal cluster-borane analogy

    International Nuclear Information System (INIS)

    Following the detailed discussion of the transition-metal cluster moiety M6(μ3-X)8 in the preceding paper, a more general account of the importance of the d electrons in transition-metal cluster chemistry is presented. The putative analogy with borane clusters (and their derivatives) is examined critically. Although an isolobal relationship exists between, e.g., BH and appropriate ML/sub n/ fragments (e.g. conical Fe(CO)3), this does not imply that the BH and ML/sub n/ fragments behave in electronically similar ways when cluster formation occurs, even when structurally related clusters are formed. Nonidentical isolobal fragments have orbital differences that manifest themselves in interfragment resonance integrals and require a qualitative distinction to be drawn between the bonding modes and detailed electronic structures of (i) transition-metal cluster compounds and (ii) boranes, carboranes, and their metalla derivatives; an analysis developed in the electronic structure theory of transition-metal systems shows why this is the case. The isolobal principle and Wade's rule owe their generality and utility to being symmetry-based statements; the energetics and details of the electronic structure of cluster compounds however are a separate matter requiring appropriate methods of theoretical chemistry. 39 references, 3 figures

  9. Carboranyl Nucleosides & Oligonucleotides for Neutron Capture Therapy Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Schinazi, Raymond F.

    2004-12-01

    This proposal enabled us to synthesize and develop boron-rich nucleosides and oligonucleotide analogues for boron neutron capture therapy (BNCT) and the treatment of various malignancies. First, we determined the relationship between structure, cellular accumulation and tissue distribution of 5-o-carboranyl-2'-deoxyuridine (D-CDU) and its derivatives D-ribo-CU and 5-o-carboranyluracil (CU), to potentially target brain and other solid tumors for neutron capture therapy. Synthesized carborane containing nucleoside derivatives of CDU, D- and L-enantiomers of CDU, D-ribo-CU and CU were used. We measured tissue disposition in xenografted mice bearing 9479 human prostate tumors xenografts and in rats bearing 9L gliosarcoma isografts in their flanks and intracranially. The accumulation of D-CDU, 1-({beta}-L-arabinosyl)-5-o-carboranyluracil, D-ribo-CU, and CU were also studied in LnCap human prostate tumor cells and their retention was measured in male nude mice bearing LnCap and 9479 human prostate tumor xenografts. D-CDU, D-ribo-CU and CU levels were measured after administration in mice bearing 9479 human prostate tumors in their flanks. D-CDU achieved high cellular concentrations in LnCap cells and up to 2.5% of the total cellular compound was recovered in the 5'-monophosphorylated form. D-CDU cellular concentrations were similar in LnCap and 9479 tumor xenografts. Studies in tumor bearing animals indicated that increasing the number of hydroxyl moieties in the sugar constituent of the carboranyl nucleosides lead to increased rate and extent of renal elimination, a decrease in serum half-lives and an increased tissue specificity. Tumor/brain ratios were greatest for CDU and D-ribo-CU, while tumor/prostate ratios were greatest with CU. CDU and D-ribo-CU have potential for BNCT of brain malignancies, while CU may be further developed for prostate cancer. A method was developed for the solid phase synthesis of oligonucleotides containing (ocarboran-1-yl

  10. Carboranyl Oligonucleotides for Neutron Capture Therapy Final Report

    International Nuclear Information System (INIS)

    This proposal enabled us to synthesize and develop boron-rich nucleosides and oligonucleotide analogues for boron neutron capture therapy (BNCT) and the treatment of various malignancies. First, we determined the relationship between structure, cellular accumulation and tissue distribution of 5-o-carboranyl-2'-deoxyuridine (D-CDU) and its derivatives D-ribo-CU and 5-o-carboranyluracil (CU), to potentially target brain and other solid tumors for neutron capture therapy. Synthesized carborane containing nucleoside derivatives of CDU, D- and L-enantiomers of CDU, D-ribo-CU and CU were used. We measured tissue disposition in xenografted mice bearing 9479 human prostate tumors xenografts and in rats bearing 9L gliosarcoma isografts in their flanks and intracranially. The accumulation of D-CDU, 1-(β-L-arabinosyl)-5-o-carboranyluracil, D-ribo-CU, and CU were also studied in LnCap human prostate tumor cells and their retention was measured in male nude mice bearing LnCap and 9479 human prostate tumor xenografts. D-CDU, D-ribo-CU and CU levels were measured after administration in mice bearing 9479 human prostate tumors in their flanks. D-CDU achieved high cellular concentrations in LnCap cells and up to 2.5% of the total cellular compound was recovered in the 5'-monophosphorylated form. D-CDU cellular concentrations were similar in LnCap and 9479 tumor xenografts. Studies in tumor bearing animals indicated that increasing the number of hydroxyl moieties in the sugar constituent of the carboranyl nucleosides lead to increased rate and extent of renal elimination, a decrease in serum half-lives and an increased tissue specificity. Tumor/brain ratios were greatest for CDU and D-ribo-CU, while tumor/prostate ratios were greatest with CU. CDU and D-ribo-CU have potential for BNCT of brain malignancies, while CU may be further developed for prostate cancer. A method was developed for the solid phase synthesis of oligonucleotides containing (ocarboran-1-yl

  11. Tratamiento del cáncer por captura neutrónica de boro: Su aplicación al carcinoma indiferenciado de tiroides Boron neutron capture therapy applied to undifferentiated thyroid carcinoma

    Directory of Open Access Journals (Sweden)

    Mario A. Pisarev

    2006-12-01

    Full Text Available El cáncer indiferenciado de tiroides es un tumor muy agresivo, de muy mal pronóstico y sin tratamiento efectivo. La terapia por captura neutrónica de boro (BNCT podría ser una alternativa para el tratamiento de esta enfermedad. Se basa en la captación selectiva de boro por el tumor y su activación por un haz de neutrones. El boro activado libera un núcleo de litio-7 y una partícula alfa, las cuales tienen una alta transmisión linear de energía (linear energy transfer, LET y un alcance de 5-9 µm, destruyendo el tumor. En estudios previos hemos mostrado que la línea celular humana de cáncer indiferenciado de tiroides (ARO tiene una captación selectiva de borofenilalanina (10BPA tanto in vitro como después de ser implantada en ratones NIH nude. También demostramos en estos animales inyectados con BPA e irradiados con un haz de neutrones térmicos, un 100% de control sobre el crecimiento tumoral y un 50% de cura histológica. En trabajos posteriores mostramos que la porfirina 10BOPP tetrakis-carborane carboxylate ester de 2,4-bis-(a,b-dihydroxyethyl-deutero-porphyrin IX cuando es inyectada 5-7 días antes que el BPA se obtiene una concentración tumoral de boro de aproximadamente el doble que el BPA solo (45-38 ppm vs. 20 ppm. La posterior irradiación con neutrones mostró un 100% de remisión completa en animales con tumores cuyo volumen pre-tratamiento era de 50 mm³ o menor. Los perros padecen CIT espontáneo, con un comportamiento biológico similar al humano, y una captación selectiva de BPA, abriendo la posibilidad de su tratamiento por BNCT.Undifferentiated thyroid carcinoma (UTC is an aggressive tumor with a poor prognosis due to the lack of an effective treatment. Boron neutron capture therapy (BNCT is based on the selective uptake of boron by the tumor and its activation by a neutron beam, releasing lithium-7 and an alpha particle that will kill the tumor cells by their high linear energy transfer (LET. In previous

  12. BE360, a new selective estrogen receptor modulator, produces antidepressant and antidementia effects through the enhancement of hippocampal cell proliferation in olfactory bulbectomized mice.

    Science.gov (United States)

    Nakagawasai, Osamu; Nemoto, Wataru; Onogi, Hiroshi; Moriya, Takahiro; Lin, Jia-Rong; Odaira, Takayo; Yaoita, Fukie; Ogawa, Takumi; Ohta, Kiminori; Endo, Yasuyuki; Tan-No, Koichi

    2016-01-15

    We have reported that the carborane compound BE360 is a novel selective estrogen receptor modulator and new therapy option for osteoporosis. The aim of this study was to explore the effects and underlying mechanisms of BE360 on depressive-like behavior and memory impairment in the olfactory bulbectomized (OBX) mice, an experimental animal model of depression and dementia. BE360 was administered subcutaneously to mice using a mini-osmotic pump for 2 weeks. Depressive-like behavior was measured as the reduced intake of a sweet solution in the sucrose preference test. Short-term memory was assessed using the Y-maze test. Cell proliferation was assessed by the analysis of cells expressing 5-bromo-2'-deoxyuridine (BrdU) uptake. The expression of phosphorylated cyclic-AMP response element binding protein (pCREB) and brain-derived neurotrophic factor (BDNF) were measured by immunoblot. The depressive-like behavior and memory impairment in OBX mice were improved by the chronic treatment with BE360. Immunohistochemical analysis showed that the number of BrdU-positive cells in the dentate gyrus of the hippocampus significantly decreased in OBX mice whereas they increased after the chronic treatment with BE360. Immunoblotting studies revealed that pCREB and BDNF were significantly increased in the hippocampus of OBX mice treated with BE360. The present study has shown that BE360 has antidepressant and antidementia effects characterized by hippocampal cell proliferation potentially activated via CREB/BDNF signaling pathways. These results indicate that BE360 may have valuable therapeutic potential against depression and neurodegenerative diseases. PMID:26497104

  13. Uptake of a nido-carboranylporphyrin by human glioma xenografts in athymic nude mice and by syngeneic ovarian carcinomas in immunocompetent mice

    International Nuclear Information System (INIS)

    A tetraphenylporphyrin bearing four dicarbollide ([B9C2H11]-) cages linked to the o-phenyl ring positions by anilide bonds, known as boronated tetraphenylporphyrin (BTPP), has been synthesized in excellent yield from tetra-(o-aminophenyl)porphyrin and carborane carbonyl chloride followed by base-assisted cage opening and ion exchange to give the highly water-soluble potassium salt. Preliminary studies showed that BTPP accumulates in liver and in a syngeneic ovarian carcinoma, but not in normal brain parenchyma, of mice infused with BTPP subcutaneously for 6 or 7 days via surgically implanted osmotic minipumps. In this study, the uptake of boron was measured in human gliomas xenografted subcutaneously to athymic nude mice in which BTPP was infused intraperitoneally or subcutaneously or both for 3 or 7 days by using similar minipumps. Immunocompetent mice bearing a syngeneic ovarian carcinoma were similarly infused to provide comparative data. Bulk concentrations of boron up to 18 μg/g of glioma and up to 45 μg/g of carcinoma were observed when up to 102 μg/g of tissue was present in the liver after 7 days of BTPP infusion. Glioma boron concentrations were increased by ∼80% on the average correspondingly greater amounts of BTPP were infused in only 3 days. Cell counts and chemical tests on blood samples from individual mice indicate that BTPP causes moderate hepatotoxicity and thromboxytopenia. This hepatohematic toxicity syndrome should be taken into account if BTPP or a similar agent is used for boron neutron-capture therapy (BNCT) of human malignancies

  14. Homoleptic borates and aluminates containing the difluorophosphato ligand - [M(O2PF2)x](y-) - synthesis and characterization.

    Science.gov (United States)

    Schulz, Christoph; Eiden, Philipp; Klose, Petra; Ermantraut, Andreas; Schmidt, Michael; Garsuch, Arnd; Krossing, Ingo

    2015-04-21

    Weakly coordinating anions (WCAs) with the difluorophosphato ligand (O2PF2) were the target of this study. Initial experiments were conducted towards the preparation of homoleptic aluminates of the well-studied [Al(OR)4](-)-type. The preparation of the initial target structure Li[Al(O2PF2)4] failed due to the remaining Lewis acidic character of the central aluminum atom. Instead, the formation of Li3[Al(O2PF2)6] and Al(O2PF2)3 was observed with hexacoordinate aluminum atoms and verified by NMR, IR and X-ray crystallography. A possible mechanism towards these compounds was postulated in the solvent induced dismutation of the tetracoordinate Li[Al(O2PF2)4]. A singly charged WCA was realized by the exchange of the central aluminum atom for boron. The [B(O2PF2)4](-) anion was prepared starting from BH3·S(CH3)2 and boron tribromide leading to the protic room temperature Ionic Liquid (IL) [H(S(CH3)2)][B(O2PF2)4] and the neat liquid Brønsted acid H[B(O2PF2)4], respectively, representing a significantly improved synthesis with regard to the first experiments of Dove et al. The basicity of the [B(O2PF2)4](-) anion and its WCA quality were investigated on the basis of the IR-spectroscopic NH-scale and the salt [H(N(Oct)3)][B(O2PF2)4] that places it better than all oxyanions and close to the carboranate based WCAs. A pathway to the solvent free pure Li[B(O2PF2)4] salt was established on a multi-gram scale with excellent purities enabling electrochemical applications (verified by NMR, IR, X-ray crystallography and cyclovoltammetry). PMID:25785817

  15. Biodistribution of a new boron compound for BNCT in an experimental model of oral cancer

    International Nuclear Information System (INIS)

    We have proposed and validated the HCP carcinogenesis model of oral cancer, a model that mimics spontaneous malignant transformation, for BNCT research in a separate study. We herein perform a biodistribution study of a lipophilic carborane-containing tetraphenylporphyrin, CuTCPH, in this model. This compound was previously tested in a model of mice bearing subcutaneously transplanted mammary carcinomas. In the present study CuTCPH was administered as a single i.p. injection at a dose of 32 μg/g b.w. (10 μg B/g b.w.) or as 4 i.p. injections over 2 days at a dose of 32 μg/g b.w. per injection. Blood (Bl) and tissue, i.e. tumor (T), precancerous tissue surrounding tumor (P), normal pouch (N), skin, tongue, cheek and palate mucosa, liver, spleen, parotid gland and brain were sampled 3, 6, 12, 24, 48 and 72 hs post-administration in the single dose protocol and 1-4 days after the last injection in the multidose protocol. Boron (B) analysis was performed by ICP-AES. The maximum ratio of B concentration for the single dose protocol was 32.7:1 for T:N and 31.8:1 for T:Bl. The B value in tumor reached a maximum of 43.8 ppm. However, the mean value of 16 ± 14.3 ppm fell short of therapeutically useful levels. The multidose protocol yielded maximum ratios of 53.33:1 for T:N and 3633.3:1 for T:Bl. The maximum absolute B value in tumor reached 106.40 ppm. The mean value in tumor 3 days post-administration was 68.02 ± 25.02. Absolute and relative maximum and average B values markedly exceeded the therapeutic threshold values. (author)

  16. Renewed first wall coating in plasma shots at the T-11M tokamak

    Energy Technology Data Exchange (ETDEWEB)

    Buzhinskij, O.I., E-mail: buzh@triniti.ru [Troitsk Institute for Innovation and Fusion Research, Troitsk, Moscow Reg. 142190 (Russian Federation); Barsuk, V.A.; Otroshchenko, V.G. [Troitsk Institute for Innovation and Fusion Research, Troitsk, Moscow Reg. 142190 (Russian Federation)

    2010-12-15

    Experimental results on boronization in situ in the tokamak T-11M plasma shots using non-toxic and not explosive metacarborane C{sub 2}H{sub 12}B{sub 10} are presented. As a result of boronization, the film with thickness up to 0.2 {mu}m at deposition rate {approx}25 nm/s was produced. The microhardness of the formed boron containing film H{sub 10} - 600, which indicates on structuredness of coating (the microhardness of the CVD B{sub 4}C films was H{sub 100} - 1800). Injection of carborane in the plasma shots has improved a stabilization of plasma filament. The impurities in wall area have been suppressed, high-vacuum characteristics of the discharge chamber were stabilized. Plasma shot duration without disruption increased essentially. At the density of n{sub e} = 1.3 x 10{sup 13} cm{sup -3}, I{sub p} = 70 kA a shot duration was 350 ms and at the density of n{sub e} = 4.65 x 10{sup 13} cm{sup -3}, I{sub p} = 70 kA was {approx}250 ms. High repeatability of experimental results has appeared. Boronization results in to an essential decrease of the volt-second consumption rate and, correspondingly, to an increase of shot duration. Developed technology opens an opportunity of practical production of renewed structured boron-carbon coatings using of plasma shots in existing large-scale tokamaks and plasma devices.

  17. Synthesis, structural characterization, and reactivity studies of 5-CF3SO3-B10H13.

    Science.gov (United States)

    Berkeley, Emily R; Ewing, William C; Carroll, Patrick J; Sneddon, Larry G

    2014-05-19

    In contrast to previous reactions carried out in cyclopentane solvent at room temperature that produced 6-TfO-B10H13 (TfO = CF3SO3), the reaction of closo-B10H10(2-) with a large excess of trifluoromethanesulfonic acid in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (bmimOTf) gave exclusively the previously unknown 5-TfO-B10H13 isomer. Experimental and computational studies demonstrated that the difference in the products of the two reactions is a result of 6-TfO-B10H13 isomerizing to 5-TfO-B10H13 above room temperature in bmimOTf solutions. Reactivity studies showed that 5-TfO-B10H13: (1) is deprotonated by reaction with 1,8-bis(dimethylamino)naphthalene to form the 5-TfO-B10H12(1-) anion; (2) reacts with alcohols to produce 6-RO-B10H13 boryl ethers (R = Me and 4-CH3O-C6H4); (3) undergoes olefin-hydroboration reactions to form 5-TfO-6,9-R2-B10H11 derivatives; and (4) forms a 5-TfO-6,9-(Me2S)2-B10H11 adduct at its Lewis acidic 6,9-borons upon reaction with dimethylsulfide. The 5-TfO-6,9-(Me2S)2-B10H11 adduct was also found to undergo alkyne-insertion reactions to form a range of previously unreported triflate-substituted 4-TfO-ortho-carboranes (1-R-4-TfO-1,2-C2B10H10) and reactions with triethylamine or ammonia to form the first TfO-substituted decaborate [R3NH(+)]2[2-TfO-B10H9(2-)], and [R3NH(+)]2[1-TfO-B10H9(2-)] (R = H, Et) salts. PMID:24785404

  18. Radiohalogenation of biomolecules. An experimental study on radiohalogen preparation, precursor synthesis, radiolabeling and biodistribution

    International Nuclear Information System (INIS)

    Radiohalogens are widely used in nuclear medicine, both as tool for diagnostic in vivo imaging, and in radionuclide therapy. This study deals with the use of radiohalogens; separation, precursor synthesis, labeling and biological behavior. The focus is on 211At and 124I, the former being a candidate for nuclide therapy and the latter potentially useful for diagnostic imaging and Auger-electron based radiotherapy. For astatine the separation, labeling and some biological behavior is described, and for iodine the latter two. Astatine was separated from an irradiated bismuth target by dry distillation. A novel cryotrap was developed for the isolation of astatine and subsequent synthesis of radiolabeled compounds. 5-[211At]astato-2'-deoxyuridine (AUdR) and N-succinimidyl-4-[211At]astatobenzoate (SAB) were synthesized in 95% respectively 90% radiochemical yields. The former is incorporated into DNA of proliferating cells and can therefore be used as an endoradiotherapeutic agent. The latter is a conjugate for the astatination of proteins. Human epidermal growth factor (hEGF) was tagged with astatine using three approaches: a) direct labeling of native hEGF, b) conjugation with SAB, and c) direct labeling of an hEGF - 7-(3-aminopropyl)-7,8-dicarba-nido-undecaborate(1-) conjugate. The overall labeling yields were 3.5% for direct labeling, 44% for SAB and 70% for the hEGF-nido-carborane conjugate. A new route to N-succinimidyl 3- and 4- [124I]iodobenzoate, two reagents for radioiodination of proteins is described affording 90% radiochemical yield. Three radioiodinated analogs of PK11195, 1-(2-chlorophenyl)-N-methyl-N-(1-methylpropyl)isoquinoline-3-carboxyam ide, a peripheral-type benzodiazepine receptor antagonist, were synthesized. All three analogs were obtained in >90% radiochemical yield. Synthesis and application of 5-[124I]iodo-2'-deoxyuridine (IUdR) is presented. The closo-dodecaborate anion was evaluated as prosthetic group for radioiodination of macromolecules

  19. The influence of hydrogen on the chemical, mechanical, optical/electronic, and electrical transport properties of amorphous hydrogenated boron carbide

    Science.gov (United States)

    Nordell, Bradley J.; Karki, Sudarshan; Nguyen, Thuong D.; Rulis, Paul; Caruso, A. N.; Purohit, Sudhaunshu S.; Li, Han; King, Sean W.; Dutta, Dhanadeep; Gidley, David; Lanford, William A.; Paquette, Michelle M.

    2015-07-01

    Because of its high electrical resistivity, low dielectric constant (κ), high thermal neutron capture cross section, and robust chemical, thermal, and mechanical properties, amorphous hydrogenated boron carbide (a-BxC:Hy) has garnered interest as a material for low-κ dielectric and solid-state neutron detection applications. Herein, we investigate the relationships between chemical structure (atomic concentration B, C, H, and O), physical/mechanical properties (density, porosity, hardness, and Young's modulus), electronic structure [band gap, Urbach energy (EU), and Tauc parameter (B1/2)], optical/dielectric properties (frequency-dependent dielectric constant), and electrical transport properties (resistivity and leakage current) through the analysis of a large series of a-BxC:Hy thin films grown by plasma-enhanced chemical vapor deposition from ortho-carborane. The resulting films exhibit a wide range of properties including H concentration from 10% to 45%, density from 0.9 to 2.3 g/cm3, Young's modulus from 10 to 340 GPa, band gap from 1.7 to 3.8 eV, Urbach energy from 0.1 to 0.7 eV, dielectric constant from 3.1 to 7.6, and electrical resistivity from 1010 to 1015 Ω cm. Hydrogen concentration is found to correlate directly with thin-film density, and both are used to map and explain the other material properties. Hardness and Young's modulus exhibit a direct power law relationship with density above ˜1.3 g/cm3 (or below ˜35% H), below which they plateau, providing evidence for a rigidity percolation threshold. An increase in band gap and decrease in dielectric constant with increasing H concentration are explained by a decrease in network connectivity as well as mass/electron density. An increase in disorder, as measured by the parameters EU and B1/2, with increasing H concentration is explained by the release of strain in the network and associated decrease in structural disorder. All of these correlations in a-BxC:Hy are found to be very similar to those

  20. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes: I. C60, C59N+ and C48N12

    Energy Technology Data Exchange (ETDEWEB)

    Xie, R; Bryant, G W; Sun, G; C.Nicklaus, M; Heringer, D; Frauenheim, T; Manaa, M R; Smith, Jr., V H; Araki, Y; Ito, O

    2003-10-02

    Low-energy excitations and optical absorption spectrum of C{sub 60} are computed by using time-dependent (TD) Hartree-Fock (HF), TD-density functional theory (TD-DFT), TD-DFT-based tight-binding (TD-DFT-TB) and a semiempirical ZINDO method. A detailed comparison of experiment and theory for the excitation energies, optical gap and absorption spectrum of C{sub 60} is presented. It is found that electron correlations and collective effects of exciton pairs play important roles in assigning accurately the spectral features of C{sub 60} and the TD-DFT method with non-hybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C{sub 60} justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C{sub 59}N{sup +} exhibits distinguishing spectral features different from C{sub 60}: (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C{sub 59}N{sup +} characterize and explain well our measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C{sub 59}N][Ag(CB{sub 11}H{sub 6}Cl{sub 6}){sub 2}]. For the most stable isomer of C{sub 48}N{sub 12}, we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C{sub 60}, and optical absorption maxima occur at 585, 528, 443, 363, 340, 314 and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C{sub 48}N{sub 12} isomers is helpful in distinguishing the isomer structures required for applications in molecular electronics. For C{sub 59}N{sup +} and C{sub 48}N

  1. The influence of hydrogen on the chemical, mechanical, optical/electronic, and electrical transport properties of amorphous hydrogenated boron carbide

    Energy Technology Data Exchange (ETDEWEB)

    Nordell, Bradley J.; Karki, Sudarshan; Nguyen, Thuong D.; Rulis, Paul; Caruso, A. N.; Paquette, Michelle M., E-mail: paquettem@umkc.edu [Department of Physics and Astronomy, University of Missouri-Kansas City, Kansas City, Missouri 64110 (United States); Purohit, Sudhaunshu S. [Department of Chemistry, University of Missouri-Kansas City, Kansas City, Missouri 64110 (United States); Li, Han; King, Sean W. [Logic Technology Development, Intel Corporation, Hillsboro, Oregon 97124 (United States); Dutta, Dhanadeep; Gidley, David [Department of Physics, University of Michigan, Ann Arbor, Michigan 48109 (United States); Lanford, William A. [Department of Physics, University at Albany, Albany, New York 12222 (United States)

    2015-07-21

    Because of its high electrical resistivity, low dielectric constant (κ), high thermal neutron capture cross section, and robust chemical, thermal, and mechanical properties, amorphous hydrogenated boron carbide (a-B{sub x}C:H{sub y}) has garnered interest as a material for low-κ dielectric and solid-state neutron detection applications. Herein, we investigate the relationships between chemical structure (atomic concentration B, C, H, and O), physical/mechanical properties (density, porosity, hardness, and Young's modulus), electronic structure [band gap, Urbach energy (E{sub U}), and Tauc parameter (B{sup 1/2})], optical/dielectric properties (frequency-dependent dielectric constant), and electrical transport properties (resistivity and leakage current) through the analysis of a large series of a-B{sub x}C:H{sub y} thin films grown by plasma-enhanced chemical vapor deposition from ortho-carborane. The resulting films exhibit a wide range of properties including H concentration from 10% to 45%, density from 0.9 to 2.3 g/cm{sup 3}, Young's modulus from 10 to 340 GPa, band gap from 1.7 to 3.8 eV, Urbach energy from 0.1 to 0.7 eV, dielectric constant from 3.1 to 7.6, and electrical resistivity from 10{sup 10} to 10{sup 15} Ω cm. Hydrogen concentration is found to correlate directly with thin-film density, and both are used to map and explain the other material properties. Hardness and Young's modulus exhibit a direct power law relationship with density above ∼1.3 g/cm{sup 3} (or below ∼35% H), below which they plateau, providing evidence for a rigidity percolation threshold. An increase in band gap and decrease in dielectric constant with increasing H concentration are explained by a decrease in network connectivity as well as mass/electron density. An increase in disorder, as measured by the parameters E{sub U} and B{sup 1/2}, with increasing H concentration is explained by the release of strain in the network and associated decrease in

  2. Thermodynamics Features of Cesium and Strontium Extraction by Mixtures of H+CCD- and PEG-400 in FS-13

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L. [Washington State University, Chemistry Department, P.O. Box 644630, Pullman, WA 99164-4630 (United States); Zalupski, P. [Washington State University, Chemistry Department, P.O. Box 644630, Pullman, WA 99164-4630 (United States); Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415 (United States); Martin, L.R.; Herbst, R.S. [Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415 (United States)

    2009-06-15

    Derivatives of the cobalt bis(dicarbollide) anion, a polyhedral metallo-carborane, have proven to be unique phase transfer reagents for solvent extraction. It has been shown that a variety of cations may be partitioned into dicarbollide-containing polar organic media. The electronic delocalization of the cobalt bis(dicarbollide) anion enhances its inert characteristics, shielding its core structure from the main chemical processes that could cause degradation. It is highly resistant to radiation damage, heat, hydrolysis and redox-driven decomposition. The substantial selectivity exhibited by chlorinated cobalt dicarbollide anions in polar organic media for cesium over other members of the alkali metal family is of particular interest for nuclear fuel processing. The attractive properties of this anion have led to significant efforts to implement dicarbollides in strategies for radioactive waste management. For example, a process for the selective removal of cesium, strontium and actinides from a variety of acidic radioactive wastes using mixtures of chlorinated derivative of dicarbollide, CCD-, polyethylene glycol (PEG-400), and octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) has been developed as the UNEX process. Mixtures of H+CCD- and PEG-400 also have received attention as a possible component of the UREX+ processes, a framework for advanced aqueous reprocessing of irradiated nuclear fuel in the U.S. As part of the EUROPART project, a substantial effort focused on the synthesis and evaluation of a variety of dicarbollide derivatives attempting to blend metal-coordinating functionalities with the CCD structure. To gain a deeper understanding of selected thermodynamic features of the CCD-PEG-400 system and thereby improve the prospects for its application, the thermochemistry of cesium and strontium partitioning in liquid-liquid systems containing chlorinated cobalt bis(dicarbollide) anion (CCD-) and polyethylene glycol (PEG-400) has been

  3. Interaction of host-guest complexes of cucurbit[n]urils with double probe guests

    Institute of Scientific and Technical Information of China (English)

    MA; Peihua; DONG; Jun; XIANG; Shuangchun; XUE; Saifeng; ZH

    2004-01-01

    [1]Freeman, W. A., Mock, W. L., Shih, N. Y., Cucurbituril, J. Am.Chem. Soc., 1981, 103: 7367-7368.[2]Day, A. I., Arnold, A. P., Method for synthesis cucurbiturils, WO 0068232, 2000, 8.[3]Kim, J., Jung, I. S., Kim, S. Y. et al., New cucurbituril homologues: syntheses, isolation, characterization, and X-ray crystal structures of cucurbit[n]uril (n = 5, 7 and 8), J. Am. Chem. Soc.,2000, 122(3): 540-541.[4]Day, A. I., Blanck, R. J, Amold, A. P., A cucurbituril-based gyroscane: a new supramolecular form, Angew. Chem. Int. Ed., 2002,41(2): 275-277.[5]Blanck, R. J., Sleeman, A. J. White, T. J. et al., Cucurbit[7]uril and o-carborane self-assemble to form a molecular ball bearing,Nano. Lett., 2002, 2(2), 147-149.[6]Liu, J. X., Tao, Z., Xue, S. F. et al., Investigation of host-guest compounds of cucurbit[n = 5-8]uril with some piperazine derivatives, Chin. J. Inorg. Chem., 2004, 20(2): 139-147[7]Zhou, Y. L., Liu, Y., Inclusion complex of β-cyclodextrin and α-aminopyridine and its assembling behavior, Science in China,Ser. B, 2004, 34(1): 68-74.[8]Ong, W., Kaifer, A. E., Molecular encapsulation by cucurbit[7]uril of the apical 4,4'-bipyridinium residuein newkome-type dendrime,Angew. Chem. Inter. Ed., 2003, 42: 2164-2167.[9]Samsonenko, D. G., Gerasko, O. A., Mitkina, T. V. et al., Synthesis and crystal structure of supramolecular adducts of macrocyclic cavitand cucurbituril with chromium (Ⅲ) and nickel (Ⅱ) aqua complexes, Russian J. Coord. Chem. (Translation of Koordinatsionnaya Khimiya), 2003, 29(3): 166-174.[10]He, X. Y., Li, G., Chen, H. L., A new cucurbituril-based metallo-rotaxane, Inorg. Chem. Commun., 2002, (5): 633-641.[11]Fedin, V. P., Sokolov, M. N., Dybtsev, D. N. et al., Supramolecular assemblies of [Mo3Se4Clx(H2O)9-x](4-x)+ with cucurbituril;complementarity control through the variation of x, Inorg. Chim.Acta., 2002, 331(1): 31-38.[12]Lorenzo, S., Day, A., Craig, D. et al., The first endoannular metal halide