3 rd International Summer School “Supramolecular Systems in Chemistry and Biology” Lviv (Ukraine), 6 - 10 September 2010

1. 3rd International Summer School “Supramolecular Systems in Chemistry and Biology” Lviv (Ukraine), 6 - 10 September 2010 _________________________________________ SUPRAMOLECULARITY OF CARBON NANOTUBES Mykola T. Kartel Chuiko Institute of Surface Chemistry, NAS of Ukraine 17 General Naumov Street, Kiev, Ukraine

2. INTRODUCTION • Supramolecular chemistry – chemistry of molecular ensembles and intermolecular bonds (J.-M. Lehn, 1978) • Other definitions: • - Chemistry outside of a molecule; • - Chemistry of non-covalent bonds • Supramolecule is a complex molecule, usually big (host), bonded other molecule (guest) • Supramolecular interactions (on energy of bond): • - Interaction ion-ionic (100-350 kJ/mol), are close to covalent bond • - Ion-dipole interaction (50-200 kJ/mol) • - Dipole-dipole interaction (5-50 kJ/mol) • - Hydrogen bond (4-120 kJ/mol) • - Cation-π-interaction (50-80 kJ/mol) • - π-π - Steking-interaction (0-50 kJ/mol) • Van-der-Vaals forces (< 5 kJ/mol)

3. Supramolecular phenomena are the interdisciplinary area: supra systems are considered in chemistry, biology, biochemistry, life sciences and materials science. Objects of consideration of supramolecular chemistry can be high disperse and high porous materials possessing a considerable specific surface area. High disperse (nanodisperse) materials with the size of particles ~ 1 nm have an external surface area >100 m2/g. High porous (nanoporous) materials with the size of holes ~ 1 nm have an internal surface area >1000 m2/g. Already the morphology (texture, structure, supramolecular structure) of such materials has character of supramolecularity (interaction of elements of a skeleton – chains, tetrahedrons, planes, globules, etc.) Atoms or the molecules adjoining a surface energetically are not compensated. It is the reason of many superficial phenomena: adsorption, heterogeneous catalysis, double electric layer, adhesion and cohesion, wetting, corrosion, capillary phenomena, flotation, surfactant action, number of biological processes. For example, system “adsorbent / adsorbate” can be considered and discussed in terms "host / guest".

4. “Classical” objects of supramolecular chemistry are carbon ones: graphite and fullerenes. For “macroobiect” graphite it is known the intercalation phenomenon by acids, salts and metals with reception of numerous inclusion compounds, thermoexfoliated graphite and also extreme display – crystal rupture on separate layers (graphene-like structures). For nanoobjects fullerenes it is known an ability to act as the guest (inclusion compounds with macrocycles of calixarenes, cyclodextrin, hydroquinon), or the host (metalorganic complexes, metallic and bimetallic complexes with properties of a superconductor).

5. SOME sp2-CARBON FORMS Graphene Graphite Nanotubes Fullerene (CNT)S. Iijima. Helical microtubules of graphitic carbon. -Nature, 1991, - V.354. - P.56-58 (SWCNT)М. Endo et al. Carbon, 1975 (MWCNT)L.V.Radushkevich, V.M.Lukjanovich.About structure of the carbon formed at thermal decomposition of carbon oxide on iron contact. –Russian J.Phys.Chem., 1952, -V.26, N1. - P.88-95 H.W. Kroto et al.C60-Buckminster-fullerene. -Nature, 1985, -V.318. -P.162-163

6. VERSIONS OF CNT SWCNT MWCNT

7. CNT are cylindrical structures with a diameter from one to several tens nm and length from several nm to several μm. They consist of one or several graphite layers with hexagonal organization of carbon atoms. Tubes come to an end with the hemispherical head formed from half fullerene. Unlike fullerenes, which represent the molecular form of carbon, CNT combine properties nanoclusters and a massive firm body that causes occurrence special, at times unexpected properties. CNT are characterized absolutely new mechanical, adsorption, optical, electric, magnetic, etc. properties.

8. SPECIFIC PROPERTIES OF CNT • Mechanical properties:strength and flexibility(hardening of metals and polymers, polymeric composites, additives to lubricants and oils, etc.); • Electronic properties:semi- and/or metallic conductivity, magnetoresistance, cold emission of electrons (electronic devices of the molecular size, information recording, diodes, field transistors, cold cathodes, materials for displays, quantum dots and wires, cathodes for X-ray radiation, electric probes, etc.); • Optical properties:resonant absorption of IR-radiation (light-emitting diodes, optoelectronic devices, thermal nanobombs); • Physical and chemical properties:developed surface and variable surface chemistry, programmed reactivity and carrier for active chemical and biological objects (sorbents, catalysts, chemical sensors, electrode materials, chemical batteries, fuel elements and supercondensers); • Biological properties:biocompatibilityand toxicity!!!,penetrationability into biological cell!!! (preparations, medical nanoinstruments, biosensors, prosthetics, means of gene engineering).

9. SCALE OF NANOSIZED OBJECTS 1 nm 1000 nm

10. METHODS OF RECEPTION OF CNT • Voltaic arc dispersion of graphite; electrolytic synthesis • Laser evaporation (ablation) of graphite; carbon epitaxy • Catalytic decomposition of hydrocarbons and carbon monoxide (CVD-technology)

11. MECHANISM OF CNT GROWTH The metal drop acts a catalyst role at formation carbon nanotube and defines its size (drawing from a site http://students.chem.tue.nl/).

12. AGGREGATES OF NANOTUBES AND NANOFIBERS The ordered and chaotic growth on substrates Kinds of nanofibers in a light microscope «Hair of water-nymph» (Moscow State University Department of Chemistry)

13. PURIFYING AND ENRICHINGCNT • Demineralization by strong acids and alkalis; • Thermoprogrammed annealing of amorphous carbon; • Thermoprogrammed wall-by-wall annealing of multi-walled tubes (enriching by single-walled tubes); • Electrolytic annealing of conducted tubes (enriching by semi-conductor tubes); • Chemical updating (increase of solubility of tubes); • Dispersion by means of ultrasound and surfactants, sedimentation separation (ultracentrifugation) individual tubes from aggregates.

14. SEPARATION OF NANOTUBES (SURFACTANTS, ULTRASOUND, ULTRACENTRIFUGE)

15. Variants of "wrapping" of nanotubes by surfactants.

16. AUTOMATED ANALYSIS OF CNT • (analysis of data received by TEM, SEM and АFМ methods) • Analysis of diameters of nanotubes • Analysis of thickness and orientation of nanofibers • Definition of length, thickness, curvature and size distribution of nanotubes • Analysis of structure of multiwalled nanotubes • Analysis of impurities in nanotubes

17. COST OF CNT PRODUCTION AND PRICES

18. COST OF CNT

19. Pilot manufacture of MW CNT on OAS “ARTEMOV TAMBOV’ ENTERPRISE “KOMSOMOLETS” Tambov, Russia Dynamics of world production of CNT (t/year) Productivity 2-2.5 t/year

20. Pilot manufacture of MW CNT on experimental section of CHUIKO INSTITUTE OF SURFACE CHEMISTRY and ENTERPRISE "ТМ-SPETSMASH“-LTD Kiev, Ukraine Installation of synthesis multiwalled CNT and CNF by CVD-method (catalytic pyrolysis of hydrocarbons). Productivity of 1-1,5 kg/day (> 0.5 t/year) TEM of CNT CARBON NANOTUBES. Specifications TU U 24.1-03291669-009:2008

21. TOXICOLOGY OF CNT RESPONSE OF ORGANISM, BODY OR TISSUE TO ACTION OF NANOPARTICLE AS DAMAGING AGENT THE FACTORS ARE CAPABLE TO LEAD TO DAMAGES IN TISSUES, BODY OR ORGANISM AS A WHOLE: • High indicator of a specific surface (i.e. the relation of the area of a particle to its weight) provides the big area of contact to cellular membranes and causes effective adsorption of substances and influences on their transport • High indicator of keeping time (low mobility in tissues, long time of deducing from an organism): more contact time - more damages • High index of reactivity: reactionary ability is interconnected with an indicator of a specific surface, heterogeneity (deficiency) of a material, and also its chemical cleanliness (for example, presence of nanoparticles of toxic metals)

22. WAYS OF PENETRATION OF CNT TO THE HUMAN BODY AND ANIMALS • At inhalation (contact to a mucous and pulmonary tissue) • Contact with skin covering • Food intake and water drinking • Intended introduction under skin, in GIТ and in blood Following action on cellular level !

23. WAYS OF CNT PENETRATION INTO CELL • PUNCTURE • PERMEATION • ENDOCYTOSIS

24. CYTOTOXICITY OF CNT

25. t min Time, min The control of barrier function of membranes and activity of mitochondria by EPR of spin probes Nitroxyl radicals in research of oxidation-reduction status of bioobjects Intensity EPR h0/h_ – Parameter of mobility of a probe, which characterizes microdensity h+ h0 h_

26. EPR-spectra of a spin probe in erythrocyte cytosol of donor blood after incubation 2 days at temperature 6 oC with CNT of various concentrations: 1 – control; 2 – 10 μg/ml; 3 – 200 μg/ml. Influence of donor blood erythrocytes incubation with CNT of various concentrations on intensity of the central component of EPR-spectrum of radicals: 1) – control; 2) – 10 μg/ml; 3) – 50 μg/ml; 4) – 100 μg/ml; 5) – 200 μg/ml.

27. Reduction of a spin probe in liver homogenate after 4 hours incubation: ♦ - control; ∆- about 200 μg/ml CNT. EPR spectra of lipophilic spin probe: in water solution; probe and expander mixes; mixes of probe, expander and CNT; probe in suspension of CNT.

28. INTERRACTION BETWEEN CNT AND NITROXYL RADICAL (preliminary quantum chemical data)

29. BIOCOMPATIBILITY OF CNT (to cells)

30. Growth of colonies of yeast cells (control) Growth of colonies of yeast cells at presence at a nutrient medium of suspension CNT

31. Kinetics of mobility (activity) of human spermatozoids in the presence of CNT in various concentrations

32. POSSIBILITIES OF MEDICAL USE OF CNT Nanocomposites with polymers and alloys (prosthetics) Internal functionalization External functionalization On the ends and defects of tubes On the walls of tubes

33. GENERAL STRATEGY OF FUNCTIONALIZATION OF CNT

34. GENERAL STRATEGY OF COVALENT FUNCTIONALIZATION OF CNT

37. IMMOBILIATION OF STREPTAVIDIN ON CNT

39. CNT AS KILLERS OF CANCER CELLS • NANOBOMBS (near IR-light) • HYPERTHERMIA (near IR-light) • DELIVERY of radioisotopes, cytochrome C, cytostatics etc. (Folic acid – provides selectivity of meeting CNT with cancer cells) Destruction of cancer cells in blood vascular with use of CNT at illumination by near IR-light (on Balaji Panchapakesan)

40. TRANSPORT OF OBJECTS INTO CELL BY MEANS OF CNT (In cytoplasm and in nucleus) • Transport of medicines (antibiotic – amphotericin B) • Transport of vaccines (peptide of virus foot-and-mouth disease virus) • Transport of proteins (streptavidin, fibrinogen, protein A, erythropoetin, apolipoprotein) • Transport of nucleic acids

41. ANTICARCINOGENIC PREPARATIONS ON THE BASIS OF PLATINUM cis - [Pt (NH3) 2Cl2)] Cisplatin Complex Pt (IV) and Complex Pt (IV) covalent connected with SWNT. Viability of tumor cells (%) at four-days influence of free complex Pt (IV) and the similar complex attached to SWNT.

42. APPLICATIONOF CNTAS CARRIERS OF BIOPREPARATES

43. NANOSENSORS (vertical oriented CNT on surface of electrode)

44. NANOSENSORS(vertical orientation of CNT on electrode)

45. NANOSENSORS(usage of CNT in form of fibers or nets) Joining of antibodies to grids from CNT allows to create nanosensors. At linkage of antibodies with a corresponding antigens (for example, the specific protein of cancer cells) changes conductivity of fibers from CNT, that is fixed by a current between electrodes. (Balaji Panchapakesan, University of Delaware, USA)

46. CONCLUSIONS: Manufacture and use of carbon nanotubes are: Expensive(small yields, special physical, chemical and biological methods of enriching, fractioning, separations, reception of great volumes with reproduced properties; the powerful and expensive equipment for the control of properties and characterization is also required); Unsafe(influence on alive organisms at cellular level and on environment; necessity to develop nanotoxicology with all expenses needed for it); Perspective(for medicine it is new class of preparations, delivery systems of medicines, vaccines, serums, a vector for gene engineering, nanosensors, nanoinstruments).

47. CONCLUSIONS • We actually use the first method of spin probes to study the cytotoxicity of nanomaterials (CNT) and the development of nanotechnology (drug delivery systems, medical biotechnology) has shown its great potential. • Advantages of the method associated with an instant assessment of the influence of parameters of the microenvironment of the probe (microviscosity, polarity, micro-relief surface, red-ox potential) on the parameters of their EPR spectra, as well as the small size of the probes (<< 1 nm), which fits well with the size range studied nanostructures and significantly less than the size of biological objects (proteins, cells, subcellular structures, etc.). • Another important aspect of the effectiveness of spin probes is that the method allows to work with very complex, optically opaque biological objects and to judge the status of their individual structures or fragments by detecting changes in the parameters of the microenvironment of the paramagnetic proper tags.

48. THANK YOU FOR ATTANTION ! БЛАГОДАРЮ ЗА ВНИМАНИЕ ! ДЯКУЮ ЗА УВАГУ !