Molekulare Maschinen und Nanomechanik

1. Molekulare Maschinen und Nanomechanik Seminarvortrag zu nanostrukturierte Festkörper Christian Kramberger Institut für Materialphysik Universität Wien

2. Outline Definition Proposed Devices Interlocked Molecules Bio-Molecules Light induced Rotation

3. Definition What is a molecular machine ? „Speaking of molecular machines isn't a metaphor. If something has moving parts and does useful work, we call it a machine. If something is nanometers in scale and has a precise arrangement of bonded atoms, we call it a molecule, or a molecular assembly. If something matches both these descriptions, we can properly call it a molecular machine; if it comprises many parts, each worthy of the name 'machine', it may be better described as molecular machine system.“ (K. Eric Drexler Trends in Biotechnology, January 1999, Vol 17 No 1, pp 5-7)

4. Visions of Nanomechanics Planetary Gear These machines consist of several thousand atoms. They are pure fiction and are pretty far beyond the current state of nanotechnology. Differential Gear Bearing http://www.imm.org

5. Some more Proposals http://www.imm.org A fine motion controller for molecular assembly A Neon selective molecular pump Interlocking joint of C structures terminated with O and N

6. NanotubeGears MD with Brenner potentials Bonds are stable up to 3000 K Slipping above 600 K Synthesis is a „future task“ working slipping (14,0) (14,0) (10,0) (18,0) http://people.nas.nasa.gov/~globus/papers/MGMS_EC1/simulation/paper.html

7. NanotubeShaft and Gear A different orientation of the Benzene teeth yields a linear motor. (14,0) (14,0) http://people.nas.nasa.gov/~globus/papers/MGMS_EC1/simulation/paper.html

8. How to Drive a NT Gear Place two elementary charges at opposite sites and apply a very high frequency electrical field (laser). The resonance frequency of this system is 140 GHz. If the laser frequency is not close to it, the NT is either switching between clockwise and counter clockwise rotation, or is just oscillating and does not rotate at all. (14,0) http://people.nas.nasa.gov/~deepak/papers/motor/paper.html

9. Driving at 140 GHz A dissipative Gear system runs stable once it has started, even with a randomly pulsed Laser as long as the system does not stop rotating. One individual NT driven NT gets due to thermal fluctuations out of phase, even at its resonance frequency. http://people.nas.nasa.gov/~deepak/papers/motor/paper.html

10. Molecular Switch Tunnel Junction a b c d + 5000 molecules per 0.007 mm2 junction. State d decay time 10-15 min.Devices are switched at+/- 2 V and read with 0.1 V. Electrical breakdown at 3.5 V. Area of 140 A2 allows rotaxanes to act individually. + - - CHEMPHYSCHEM 2002, 3, 519-525 Tetrathifullfalene TTF Dioxynaphthalene DNP dumpbell tetracationc Cyclophane

11. Junction Characteristics Hysteresis of an individual junction. Switching and reading a bit for 35 cycles. CHEMPHYSCHEM 2002, 3, 519-525 black line: 0.007 mm2 junction with approximately 5000 moleculesred line : control junction with pure dumpbells (no rings)

12. Biological Molecular Machines Nature provides a wide spectrum of transport molecules.We will focus on conventional Kinesin from bovine brains. Structure of Kinesin nature Vol. 389 p561-567 (1997)

13. Kinesin Transport Motor-Proteins move along cytoskeletal filaments driven by ATP. Kinesin is one of them and moves along cellular microtubuli. In laboratory the transport mechanism is run under reversed conditions. Layers of Kinesin can move randomly orientated microtubuli forward with 800 nms-1. http://faculty.washington.edu/hhess/index_files/slide0001.htm

14. Directed Motion 3 mgl-1 At a medium concentration of Kinesin attached to a share-deposited PTFE Film. Parallel tracks of Kinesin lead to directed motion. Scale bares are 10 mm. Microtubuli are sampled every 5 s colored from red to violet. medium concentration high concentration 0.5 mgl-1 18 mgl-1 nanotechnology 10 (1999) 232-236

15. Control of Motion Motion is powered by ATP. So the issue is controlling the concentration of ATP. Caged ATP can be released by irradiation with UV light. An ATP consuming enzyme then quickly depletes the free ATP storage. single step 4-6 mm ATP lasts for 105 cycles (without Hexokinase) nano letters 2001 vol. 1, no. 5, 235-239

16. Transporting Cargo The interaction between Kinease and microtubuli is restricted to their contact sides. The free sides of the microtubuli can be used to bind (load) cargo. This has been demonstrated with Streptadavin coated polystyrene particles. Microtubule giving a particle a lift. nano letters 2001 vol. 1, no. 5, 235-239

17. Motor Type I proc nat acad sci usa Vol 99, Iss8, pp4945-4949 Above 60 °C and irradiation with l > 280nm the left and right identical parts rotate continuously around the central C=C bond. a b d c (3R,3´R)-(P,P)-trans-1,1´,2,2´,3,3´,4,4´,-octahydro,3,3´,dimethyl-4,4`,biphenantrylidene

18. Motor Type I in E7-LC Film A LC film was doped with (6%) 6a and then irradiated withl > 280 nm at RT. The 6a turned into 6d and increased spacing between the E7 (LC) molecules.After heating the activated thickened film the motor cycle was completed.Thus the motor works in an LC environment. 0s 10s 20s 30s 40s 80s proc nat acad sci usa Vol 99, Iss8, pp4945-4949

19. Sketch of the effect on E7-LC 6a 6b 6d LC proc nat acad sci usa Vol 99, Iss8, pp4945-4949

20. Motor Type II Napthothiopyran Thioxanthene Type II has a distinct lower and upper part. The lower part can be attached to other molecules or surfaces. a b d c j am chem soc Vol 124, Iss 18, pp5037-5051

21. Rotation of Motor Type II The upper part rotates counter clock wise to the lower one. Placing different atoms or groups at the sites X and Y affects the energy barrier for the thermal induced isomer transition. Thus the speed of rotation becomes tunable. d a j am chem soc Vol 124, Iss 18, pp5037-5051

22. The End Congratulations you have just survived my talk. Thanks to anyone that is still awake and reads this and shame on anyone else!

23. Literature A DNA fuelled molecular machine made of DNA Bernard Yurke, Andrew J. Turberfield, Allen P. Mills Jr., Friedrich C. Simmel, Jennifer L. Neumann nature vol 406 p605-p608 10.08.2002 Molecular motors: structural adaptions to cellular functions Joe Howard nature vol 389 p561-p567 09.10.1997 Light-Controlled Molecular Shuttels Made from Motor Proteins Carrying Cargo on Engineered Surfaces Henry Hess, John Clemmens, Dong Quin, Jonathan Howard, Viola Vogel nano letters 2001 vol. 1, no. 5 235-239 21.02.2001 Molecular shuttels: directed motion of microtubulus along nanoscale kinesin tracks John R Dennis, Jonathan Howard, Viola Vogel nanotechnology 10 (1999) 232-236 01.09.1998 Molecular Shuttels based on Motor Proteins Henry Hess, John Clemmon, Robert Doot, Johnathon Howard, Viola Vogel Ninth Foresight Conference on Molecular Nanotechnology Light-driven molecular switches and motors Feringa BL, Kommura N, Van Delden RA, Ter Wiel MKJ appl phys a mat sci progress Vol 75, Iss 2, pp 301-308 Second generation light-driven molecular motors. unidierectional motion controlled by a single stereogenic center with near perfectphotoequlibria and acceleration of the speed of rotation by structural modification Koumura N, Geertsema EM, van Gelder MB, Meetsma A, Feringa BL j am chem soc Vol 124, Iss 18, pp5037-5051 Unidirectional rotary motion in a liquid enviroment: Color tuning by a molecular motor van Delden RA, Koumura N, Harada N, Feringa BL proc nat acad sci usa Vol 99, Iss8, pp4945-4949 Building Molecular Machine Systems K. Eric Drexler Trends in Biotechnology, January 1999, Vol 17 No 1, pp 5-7. A Phenomenological Model of the Rotation Dynamics of Carbon Nanotube Gears with Laser Electric FieldsDeepak Srivastavahttp://people.nas.nasa.gov/~deepak/papers/motor/paper.html Two-Dimensional Molecular Electronics CircuitsYi Luo, C. Patrick Collier, Jan O. Jeppeson, Kent A. Nielson, Erica Delenno, Greg Ho, Julie Perkins, Hsian-Rong Tseng, Tohru Yamamoto, J, Fraser Stoddart, and James R. HeathCHEMPHYSCHEM 2002, 3, 519-525 Institute of Molecular Manufactoring http://www.imm.org Molecular Dynamics Simulations of Carbon Nanotube Based GearsJie Han and Al Globus, MRJ, Inc., Richard Jaffe, NASA, Glenn Deardorffhttp://people.nas.nasa.gov/~globus/papers/MGMS_EC1/simulation/paper.html