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Handling molecular machines by our hands: beyond Nobel Prize and Nanotechnology.

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Handling molecular machines by our hands: beyond Nobel Prize and Nanotechnology.

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Plenary lecture given by Prof. Katsuhiko Ariga (WPI-MANA, NIMS and University of Tokyo, Japan) on September 12, 2017 in Gramado (Brazil) during the XVI B-MRS Meeting.

Plenary lecture given by Prof. Katsuhiko Ariga (WPI-MANA, NIMS and University of Tokyo, Japan) on September 12, 2017 in Gramado (Brazil) during the XVI B-MRS Meeting.

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Handling molecular machines by our hands: beyond Nobel Prize and Nanotechnology.

  1. 1. 1 Handling Molecular Machines by our Hands beyond Nobel Prize and Nanotechnology Katsuhiko Ariga WPI-MANA, National Institute for Materials Science (NIMS) & Graduate School of Frontier Sciences, The University of Tokyo
  2. 2. Thank you very much for kind invitation
  3. 3. I am very happy.
  4. 4. Anyway ……
  5. 5. Molecular Machines Got Nobel Prize!
  6. 6. Dr. Sauvage Dr. Stoddart Dr. Feringa
  7. 7. Molecular Machine Manipulation by Nanotechnology
  8. 8. Dr. Hill Nano Lett. 15, 4793 (2015). Top-Level Nanotechnology with Future Success Current-driven Supramolecular Motor with In-situ Surface Chiral Directionality Switching
  9. 9. "Nanocar Race" Car race that use a single molecule as a car
  10. 10. Drivers gear up for world’s first nanocar race Nature, 544, 278 (2017)
  11. 11. 6 Teams from 6 Countries Sponsor: PSA Peugeot Citroen Sponsor: Swiss Nanoscience Institute Sponsor: TOYOTA Sponsor: Volkswagen Die Gläserne Manufaktur Car Car Car Rotor Rotor ???
  12. 12. NIMS-MANA nanocar Conformation-Car O O O O 2.1 nm 0.93 nm 0.81 nm 0.28 nm
  13. 13. 1 nm That's one small step for a molecule, one giant leap for mankind.
  14. 14. Race for JAPAN Team 1st DAY 11:00 Race started 11:10 First pulse, 1 nm run 11:15 Software crash Destroy of Tip, Race tracks, and Nanocars 11:30 Stop of the race 13:00 Recovery of the software and restart of the race ...Trials to make the Flat nanocars and re-shape of the tip day and night... 2nd DAY 6:30 Software crash AGAIN, JAPAN Team retired.
  15. 15. Race Records ~1000 nm?
  16. 16. Working Day and Night Fair Play Prize for NIMS-MANA JAPAN Team
  17. 17. Beyond Nobel Prize & Nanotechnology
  18. 18. Freely tune molecules just by our hands Hand-Operating Nanotechnology Beyond Nobel Prize & Nanotechnology More general & versatile
  19. 19. Necessary forces to control molecules
  20. 20. Necessary forces to control molecules 1 10 100 1000 10000 pN Chemical bond: C-O (calcd; 4300 pN) ref1 C-C (calcd; 4120 pN) ref1 C-N (calcd; 4100 pN) ref1 C-Si (2000 pN) ref1 covalent bond in carbonic anhydrase B unfolding (1700 pN) ref 2 S-Au (1400 pN) ref 1 Weak covalent bond: quadruple H-bonded ureido- 4[1H]-pyrimidinone (UPy) system (148 pN) ref3 C-O carboxyl groups (in vaccum, Hex, 1-PrOH, clcd; 148, 144, 71, 57 pN) ref 4 O-H carboxyl groups (in water, clcd; 17 pN) ref 4 Strong protein interactions: Antigen/Antibody (224, 160, 120, 55 pN) ref 5, 7, 9, 17 Biotin/Streptavidin (160, 150, 55 pN) ref6, 8, 16 Biotin/Avidin (130, 50 pN) ref8, 18 PDZ domain/recognition peptide (120 pN) ref 10 P-selectin/PSGL-1 ligand (115 pN) ref 11 p53/mdm2 (105 pN) ref 12 DNA assembly: Melting of dsDNA into single strands (150 pN) ref 37 B to S form (65 pN) ref 38 phi DNA packing motor (57 pN) ref 39 Adenine/Thymine (54 pN) ref 40 RNA polymerase stalling (25 pN) ref 41 Unzipping of poly(dG-dC), inhomogeneous, poly(dA-dT) DNA (20, 12, 9 pN) ref 37, 42 Straighten (6 pN) ref 43 Conformational change of protein: Stretching alpha-helix (200 pN) ref44 Unfolding of ubiquitin (160 pN) ref 45 Unfolding of fibrinogen (94 pN) ref 94 Small force: Force to produce energy 1kT by pull of 1nm at 300K (4 pN) ref 47 Force by membrane potential per elementary charge in protein pore (3 pN) ref48 Moderate protein interactions: Azurin/cytocrom c551 (95 pN) ref 13 p53/azurin (75 pN) ref 14 Carbonic anhydrase/inhibitor (65 pN) ref 15 Alpha-beta integrin/GRGDSP (20 pN) ref 19 Thrombin/aptamer (5 pN) ref 20 Unfolding of alpha-helical protein (50 pN) ref 29 Unfolding of a single Ankyrin repeat (37 pN) ref 26 Cadherin-Cadherin complex (35 pN) ref 30 Refolding single Ankyrin repeat (32 pN) ref 26 Unfolding of myosin II (31 pN) ref 31 Weak protein interactions: gating spring of channel (10 pN) ref 32 Kinesin stall force on microtubule (7 pN) ref 33 Focal adhesion and cytoskeleton (1 pN) ref 34 cell-cell contacts (1 pN) ref 35 Force detectable by hair cell bundle (1 pN) ref 36 Myosin V 3 pN RNA polymerase 23 pN azobenzene 1000 pN N N N O spiropyran 2000 pN References from Anishkin et al. PNAS, 2014, 111, 7899 and others.
  21. 21. How to control a molecule: Unexplored region 1 10 100 1000 10000 pNMyosin V 3 pN RNA polymerase 23 pN azobenzene 1000 pN N N N O spiropyran 2000 pN Not well-controlled by external forces DNA RNA unzipping 0.5-15 pN F0F1-ATPase 8 pN Conformation/ Interactions/ Soft Bio-Control Photo isomerization/ Covalent bond formation Force Mechano-chemistry Conventional operations
  22. 22. Small Forces (pN) for Bio-functions D. G. Rodriguez et al. Science, 2012, 338, 910. D. E. Discher et al. Science, 2005, 318, 1139. M. P. Sheetz et al. Science, 2009, 323, 638. Cell migration (infiltration of cancer) Cell differentiation (ES/iPS) Protein conformational change (change in ligand binding and enzymatic activity) …. artificial controls under challenges
  23. 23. Molecule/Nano Macroscopic Materials ScienceNanotechnology Size-Increase (Assembly) Reduce Dimension: 3D to 2D Macroscopic Molecule/Nano Nanotechnology & Materials Science
  24. 24. Surface pressure (F): 1-70 mN/m Estimated force per molecule ≅ 0.5-35 pN Estimated pressure ≅ 0.5-35 MPa Estimated energy (integral of π-A curve) ≅ 1 kcal/mol Thermal fluctuation occurs when energy barrier is under 20 kcal/mol. Oki, M. Proc. Jpn. Acad., Ser. B 2010, 86, 867–883. Force/Energy at the Air-Water Interface: Langmuir Monolayer System 0 10 20 30 40 50 0.3 0.6 0.9 1.2 1.5 1.8 Surfacepressure[mNm–1] Molecular area [nm2] Eintegral=~1 kcal mol-1 30 1 2 0 1 0 Mechanical Energy Eintegral
  25. 25. Langmuir technique can cover unexplored region 1 10 100 1000 10000 pNMyosin V 3 pN RNA polymerase 23 pN azobenzene 1000 pN N N N O spiropyran 2000 pN Well-controlled at the air-water interface DNA RNA unzipping 0.5-15 pN F0F1-ATPase 8 pN Conformation/ interactions Photo isomerization/ Covalent bond formation Mechano-chemistry
  26. 26. Breaking Common Sense to Create A New Road First Demonstration Catch & Release A Molecule by Our Hand Motions
  27. 27. Molecular Machine at Dynamic Interface Macroscopic Dimension Monolayer at Dynamic Interface Molecular-level Dimension Environment with both molecular and macroscopic characteristics! Dynamic but Flat Invisible molecular machines Active Film Molecular machines have got Nobel Prize! Useless ??? Nanocar under vacuum
  28. 28. 28
  29. 29. 29
  30. 30. 30
  31. 31. 31
  32. 32. 32 Bulk Operation Access to Molecular World Connection between molecular (nano) world and real (visible) world Hand-Operating Nanotechnology Molecular Machine at Interface
  33. 33. Breaking Common Sense to Create A New Road Second Demonstration Tuning of Receptors New Mode of Molecular Recognition Tuning Receptor
  34. 34. Second Demonstration Finer Tuning of Receptors Precise Discrimination of Biomolecules by Mechanical Motions New Mode of Molecular Recognition Tuning Receptor
  35. 35. J. Am. Chem. Soc., 128, 14478 (2006). Phys. Chem. Chem. Phys., 13, 4895 (2011). Hand-Operating Nanotechnology Chiral Resolution by Hand Motion First Achievement Since Dr. Pasteur
  36. 36. J. Am. Chem. Soc., 132, 12868 (2010). Surface Pressure / mNm-1 BindingConstant(KU/KT) [LiCl] = 0 mM [LiCl] = 10 mM Best Condition
  37. 37. Traditional Host-Guest Systems Simple Use of Energy Minimum Mechanism for Most of Molecular Machines (2nd Nobel prize) Continuous Modulation to Find Best Solution from Numerous Candidates Mechanical Tuning of Conformation of Host Molecule Energy Energy Hand-Operation One State Tuning Use soft materials softly. Pioneer: S. Shinkai et al., Tetrahedron Lett. (1979), Chem. Lett. (1980), Chem. Commun. (1980), JACS (1981) Switching Switching between Separate States Energy Origin of Supramolecular Chemistry (1st Nobel prize)
  38. 38. New concept may come Functional Conformer Science Tuning molecules toward best function at outside of simple equilibrium All possible conformers Unexplored functions Huge possibilities So far, we only investigated most stable and most probable state
  39. 39. Breaking Common Sense to Create A New Road How is energy efficiency of Hand-Manipulation of Molecule at interface? Exploration with model system
  40. 40. 0 10 20 30 40 50 60 70 80 90 100 Energy efficiency: High efficiency with simple direct contact of force and motion. Can we extend this assumption to molecular-level? Molecular- Level ?
  41. 41. Simple mechanical molecular machine Hydrophobic alkyl chain Hydrophilic polyether chain OO O O O O O O Dr. Waka Nakanishi
  42. 42. Recent Work: Mechanochemical Control of Simple Molecular Machine, a Nano-Pliers Compression Expansion Angew. Chem., Int. Ed., 54, 8988 (2015). Hydrophobic alkyl chain Hydrophilic polyether chain
  43. 43. Theory & Experiments Revealed Motion of a Molecule Hydrophobic alkyl chain Hydrophilic polyether chain 1 mN/m 10 mN/m 20 mN/m 30 mN/m 2.0 1.0 0 − 1.0 − 2.0 200 250 300 350 λ /nm θA/mdegnm2 3.0 − 3.0 Force 200 250 300 350 λ /nm 600 400 200 0 − 200 − 400 − 600 − 800 800 − 90° ∆ε/M-1cm-1 − 80°− 70°− 60°− 50° Close of pliers Experimental data from transferred monolayer Simulations of single molecule TDDFT(B3LYP/6-31Gdp)
  44. 44. MD Simulations Revealed Structures of Molecules in an Assembly Expanded Compressed Dr. D. Cheung, National University of Ireland Galway Hydrophobic alkyl chain Hydrophilic polyether chain
  45. 45. Energy given at the air-water interface 0.5 1 10 20 30 40 0 Molecular Area / nm 2 SurfacePressure/mNm -1 Energy by Thermodynamics
  46. 46. Characteristic Properties at the Air-Water Interface 3 Estimated φ and obtained torsional energies v.s. applied mechanical force Control of conformational change of molecules and proteins is possible. Efficient energy conversion is expected. molecule
  47. 47. 0 10 20 30 40 50 60 70 80 90 100 Electricity generation Machines at macro size Machines at nano size Mechanical molecular machine works with high efficiency. N N Direct mechanical driving is best method.
  48. 48. Unified Understanding on Relation between Force and Motion from MACRO to NANO
  49. 49. Comparison of Forces [N] Myosin V 3 pN RNA polymerase 23 pN Macroscopic Molecular Machine Car 45 kN Biology Size 1 m 10 nm 1 nm ac F0F1-ATPase 8 pN Binaphthyl 1 pN Binaphthyl +Lipid Matrix 1 pN Interfacial Mechanical Molecular Machine Human 8 kN Beetle 10 N
  50. 50. Weight/Force x Length [g/Nm] Operated weight per energy Traditional Molecular Machines Interfacial Molecular Machines Biology Macroscopic Machines 1000 100 10 1 0.1 0.01 0.001 0.0001 [g/Nm] nm µm mm m Size Car Human Beetle ATPase Myosin V RNA Polymerase Stilbene Spiropyran
  51. 51. Breaking Common Sense to Create A New Road Next Challenges Control of Life by Hand-Operating Nanotechnology
  52. 52. DNA Origami Dr. Yonamine Collaboration with Prof. Murata (Tohoku Univ.)
  53. 53. DNA Origami fold M. Endo et al. Biomater. Sci., 1, 347 (2013)
  54. 54. Shape-forming and assembly of DNA origami is pre-determined (programed) with DNA sequence. Concept of DNA Origami We want to control them by our hands beyond program.
  55. 55. 7,249 base Cationic lipid Lipid-modified DNA origami sheet 90 nm 65nm DNA origami sheet ss DNA M13 mp18 Staple DNA strands Langmuir Film of Lipid-modified DNA Origami Sheet 1-D fusion Air-water interface Langmuir film Compression Expansion
  56. 56. Langmuir-Blodgett Film of DNA Origami
  57. 57. Lipid (2C18N+) Lipid-modified DNA sheet π-A isotherm and AFM Image of Lipid-DNA Origami Sheet Lipid-modified DNA origami sheet DNA origami sheet 1.0 nm1.5 nm 200 nm 200 nm 32 mN/m First Example of DNA Origami LB Film
  58. 58. Repeat Compression and Expansion (3 ⇄ 30 mN/m) Air-water interface Langmuir film Compression Expansion ? Transfer at 32 mN/m
  59. 59. 1000 nm 0 repeat Pressure[mN/m] 0 3 30 Time 32
  60. 60. 1 repeat 1000 nm Pressure[mN/m] 1 3 30 Time 32
  61. 61. Belt-shape fusion 2 repeat 1000 nm Pressure[mN/m] 3 30 Time 2 32
  62. 62. 0 nm 93 nm 68 nm 74 nm 1740 nm H L W L / H Aspectratio W / H 1500 500 1000 0 0 2 Number of cycle 0 2 20 10 0 30 L / W 0 2 500 nm 0 repeat 2 repeat 500 nm Supramolecular Polymerization of DNA Origami Phys. Chem. Chem. Phys. 2016, 18, 12576–12581.
  63. 63. Cell Differentiation Cell Fate Control at Interfaces.
  64. 64. Fluidity of Microenvironment 64Uto, K. & Ebara M. et al. ACS Biomater. Sci. Eng. 2016, 2, 446–453. Fluid for cellular microenvironment
  65. 65. Stiffness of Biological Tissues 65Engler A. J. et al. Cell 2006, 126, 677–689. Super-Hard Super-Soft
  66. 66. Super Hard! Fullerene Crystals 66 • 1D fullerene crystal • Uniform structure with high aspect ratio – ca. 500 nm in diameter – > 100 µm in length • Biocompatibility – Phagocytosis by macrophage-like cell – Low cytotoxicity 1 µm Adv. Biomed. Res. Proceedings 2010, 89. J. Mater. Res. 2002, 17, 83. whisker sheet Fullerene Whisker / Nanowhisker Liquid–Liquid Interface Precipitation (LLIP) method Crystals grow at liquid–liquid interface. • Various structure
  67. 67. Alignment of Fullerene Whiskers 67 FW film Compress Transfer Dry Aligned FW film Aligned FW 2.5 µm20 µm 500 nm Optical microscopy SEM Atomic force microscopy Langmuir–Blodgett (LB) approach Adv. Mater. 2015, 27, 4020–4026. Dr. Minami Mr. Kasuya
  68. 68. Elongation of Cell Morphology by FW Pattern 68 Bare glass Random FW Aligned FW Fluorescent analysis of cell morphology Stain: Cytoskeleton/Nuclei 100 µm Aspect ratio of cells Myoblast Elongated shape Early stage of myogenesis Aligned FW induced early stage of myogenesis, and controlled the growth direction of myoblasts. 2.3 4.0 Adv. Mater. 2015, 27, 4020–4026.
  69. 69. Promotion of Differentiation 69 Myogenesis under low serum environment Aligned FWBare glass Gene expression Fusion index Cell adhesion Morphology Differentiation Elongation Fusion Aligned FW induced myogenic differentiation. Stain: Myosin heavy chain/Nuclei Adv. Mater. 2015, 27, 4020–4026.
  70. 70. Super Soft! Liquid–Liquid Interfaces 70 Liquid–Liquid interfaces • Fluid environment Perfluorocarbons • Fully fluorinated substances • Immiscible with water as well as common organic solvents • Heavier density than water Perfluorocarbon Water From wikipedia RfOct RfMCH RfPh Dr. Minami
  71. 71. Spreading and Morphological Investigations 71 Cells at RfOct interface only showed spreading morphology. ACS-AMI Accepted Spreading
  72. 72. Suppression of Differentiation 72 Myogenic differentiation can be suppressed by fluid microenvironment.
  73. 73. Can interfaces determine cell fate? 73 Stemness maintenance Cell Death Differentiation 2010, 17, 1230–1237. Unstable iPS cells • iPS cells have pluripotency. – Easy to differentiate – Necessary to maintain their pluripotency • Stemness maintenance Interfacial culture
  74. 74. How to control molecule, systems, & life 1 10 100 1000 10000 pN Myosin V 3 pN RNA polymerase 23 pN azobenzene 1000 pN N N N O spiropyran 2000 pN Not well-controlled by external forces New Challenge DNA RNA unzipping 0.5-15 pN F0F1-ATPase 8 pN Conformation/ Interactions/ Soft Bio-Control Photo isomerization/ Covalent bond formation Force Mechano-chemistry Conventional operations
  75. 75. Write Delete Rewrite C60 molecule Bit density: 200 Tb/in2 Monomolecular level ultrahigh density memory Atomic Switch High-Tech-Driven Nanotechnology Hand-Operating Nanotechnology Easy-Action-Based Nanotechnology Nanotechnology for Common Use in Daily Life However …………. They are only operations under selected conditions with specialized equipment
  76. 76. Thank you very much Members Antonio Robson Andrei

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