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A.I.Konovalov

A.I.Konovalov. Supramolecular Systems Are The Bridge From The Inanimate To Living Matter 3 th Internationl Summer School « Supramolecular Systems in Chemistry and Biology » 6-10 September 2010, Lviv , Ukraine. Big History Универсальная история. Our Time. Big Bang. Pre-biological

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A.I.Konovalov

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  1. A.I.Konovalov Supramolecular Systems Are The Bridge From The Inanimate To Living Matter3thInternationl Summer School «Supramolecular Systems in Chemistry and Biology» 6-10 September 2010, Lviv, Ukraine

  2. Big History Универсальная история Our Time Big Bang Pre-biological Evolution Biological Evolution Social Evolution

  3. J.-M. Lehn 1978 г. Supramolecular chemistry may be defined as “chemistry beyond the molecule”, bearing on the organized entities of higher complexity that are resulted from the association of two or more chemical species held together by intermolecular forces. Supramolecular systems are the selforganized entities that are resulted from the association of two or more molecules held together by intermolecular forces(noncovalent bonds).

  4. Covalent bond Ion-ion interaction Ion-dipole interaction Dipole-dipoleinteraction Hydrogen bond Cation –n(π)interaction π-π interaction Van-der-Waals interaction Hydrophobiceffects 200-300 kJ/mol 50-200 kJ/mol 5-50 kJ/mol 4-120 kJ/mol 5-80 kJ/mol 0-50 kJ/mol (<5 kJ/mol) Entropy Nature of the intermolecular forces

  5. Supramolecular A….. A A …… BSupermolecules systemsA ……B ….. C Supramolecular C ….. Aassemblies non-covalent bonds (intermolecular) The hierarchy of structural organization of matter Atomsa b c MoleculesA(a-a) B(a-b) C(b-c) covalent bonds Biological Community of mutually dependent functionally different systems supramolecular systems

  6. Two approaches will be usedinthis lecture 1) architecture-functional comparison of synthetic and natural supramolecular systems 2) energetic analyses of levels of the hierarchy of structural organization of matter

  7. TWO WAYS IN STUDY OF SUPRAMOLECULAR SYSTEMS 1 – SYNTHETIC SUPRAMOLECULAR SYSTEMS Investigation of supramolecular systems of different architectures with different functions created on the base of synthetic components 2 – NATURAL SUPRAMOLECULAR SYSTEMS Investigation of architectures and functions of supramolecular systems and their components separated from biological objects

  8. O O O O O O K+ Cation Receptors Ch.J.Pedersen 1967 Dibenzo-18-crown-6 yield 0.4%

  9. O O CH3 O O O O O M e O + + O O K K CH3 M e O O O O + K O O O O O CH3 К+ O CH3 • Cation receptors K = 106 18-crown-6 К – insignificantly small ! Macrocyclic effect Preorganization Multipoints binding Cooperativety K = 102 podand

  10. O O O O O + K + N N K O O O O O O O J.-M.Lehn 1969 K = 106 K = 1010 Macrobicyclic effect Logarithms of the binding constants Binding selectivity Molecular recognition Molecular informatics d ion 1.36 ǺLi+ 7,54,02,0 1.90 ǺNa+6,09,07,0 2.66 ǺK+ 2,06,510,0

  11. Recognition of s-, p- and d-metal cations I.S.Antipin, I.I.Stoikov A.I.Konovalov2007 Е% R: 1 2 3 a) cone cations 4 b) paco c) 1,3 alt 5

  12. Anion receptors HSO4-и H2PO4- HSO4- ,CH3COO-и ReO4- TcO4- J.L.Sessler B.F.MyasoedovYu.A.Ustinyuk 2007

  13. Neutral molecules binding

  14. The role of hydrogen bonds Acetic acid dimer Übermoleküle Melamine - cyanuric acid Complementarity: - spatial - functional

  15. Strip Rosette SELF-ORGANIZATION G.M.Whitesides 1995

  16. J.M.Lehn SELF-ORGANIZATION Cu+ Self-recognition !

  17. 9 + M e M e M e M e N N N N M e M e + N N N N N N A g N N N N N N N N + M e M e 6 9 N N N N N N N N N N N N N N N M e M e N N N N N N N N N M e e M e M e M Self-organization of supramolecular architecures 3.3 нм • NANOCYLINDER from: • Linear molecules • Plane molecules • 12 CationsCu(I)

  18. Self-organization of supramolecular architecures 18

  19. SELF-ORGANIZATION OF AMPHIPHILIC COMPOUNDS

  20. Transport metal complexes through liquid chloroform membrane R=C9H19 CHCl3 Receiving phase H2O Giving phase H2O H+ H+

  21. 22 Transport of compounds from bibliotheka of di-, hydroxy- and amino-acids. РМ3 model of complex of calixarene 22 with oxalic acid

  22. O O H H R R Transport of compounds from bibliotheka of di-,hydroxy- and amino-acids 

  23. Supramolecular catalyst Supramolecular system – amphiphilic calix[4]resorcinearenes - surfactant - La(III) I.S.Rizhkina A.I.Konovalov 2005. 170 000 times!

  24. 1 – SYNTHETIC SUPRAMOLECULAR SYSTEMS Investigation of supramolecular systems of different architectures with different functions created on the base of synthetic components 2 – NATURAL SUPRAMOLECULAR SYSTEMS Investigation of architectures and functions of supramolecular systems and their components separated from biological objects

  25. The role of hydrogen bonds Acetic acid dimer Übermolekül Melamine - cyanuric acid Complementarity: - spatial - functional

  26. Adenine Thymine Cytosine Guanine HYDROGEN BINDING OF NUCLEOTIDE BASES Chemical informatics Information storageon molecular level but Information readout on supramolecular level

  27. H H N C N O C N H C C C N O H P O N O O O H N O N H N O P O N N O H O O O N N O O P O O O H H N O N O N O P O O O O O O P O DNA DOUBLE SPIRAL ADENINE GUANINE THYMINE CYTOSINE

  28. DOUBLE SPIRALS

  29. O O O O O O IONPHORES Valinomicine 18-crown-6 АМPHIPHILES

  30. Both: in flasks and in biological systems receptor – substrate substrate selectivity molecular recognition molecular informatics transport (ions, molecules) catalysis selforganization architecture

  31. Genetic apparatus: DNA Externalcytoplasmic membrane: Amphiphilic lipids, proteins Biosynthetic apparatus: mRNA, ribosomes, тRNA Metabolic apparatus: proteins; enzyme products substrates PROCARIOTE CELL

  32. МEMBRANE WORLD supramolecular RNA WORLD supramolecular POLIPEPTIDE WORLD supramolecular ENZIME WORLD supramolecular ____________________ SUPRAMOLECULAR WORLD

  33. «With one or two exceptions, biological materials are “soft”, that meaning they combine viscous and elastic elements. This mechanical behavior results from self-assembled supramolecular structures that are stabilized by noncovalent interactions.»

  34. IN PROCESS OF EVOLUTION (BIG HISTORY) SUPRA-MOLECULAR SYSTEMS HAVE APPEARED JUST AFTER APPEAREHCE OF MOLECULES NOT BIOLGICAL SYSTEMS HAVE BEGUN SUPRAMOLECULAR SYSTEMS ON THE CONTRARY COMMUNITY OF SUPRAMOLECULAR SYSTEMS HAS BEGUN BIOLOGICAL SYSTEMS

  35. MAY BE MORE RIGHT Nature used properties of supramolecular systems for creation of biological systems But nature have not goal self- Biological systemsare resultof organization of supramolecular systems

  36. Genetic apparatus: DNA Externalcytoplasmic membrane: Amphiphilic lipids, proteins Biosynthetic apparatus: mRNA, ribosomes, тRNA Metabolic apparatus: proteins; enzyme products substrates PROCARIOTE CELL

  37. Biological systems are result of self-organization of supramolecular systems Supramolecular systems are result of self-organization of molecules Molecules are result of self-organization of atoms Atoms are result of self-organization of elementary particles ___________________________ Self-organization is spontaneous formation of definite ordered systems

  38. Ability to self-organizationisfundamentalproperty of matter Paul Davies, The Cosmic Blueprint, 2004 Hermann Haken, Erfolgsgeheimnisse der Natur, 1992 Ilja Prigogine, From Being to Becoming, 1980 Jean-Marie Lehn, Toward Self-Organization and Complex Matter, 2002

  39. Atoms are more complex than elementary particles Molecules are more complex than atoms Supramolecular systems are more complex than molecules Biological systems are more complex than supramolecular systems Matter develops in direction of greater complexity «Toward complex matter» J.-M. Lehn: P.Davies: «Continued unwrapping of organized complexity into Universe is fundamental property of nature» «Universe is able to creative one-directed movement ahead even in front of faceof second low»

  40. Supramolecular A….. A A …… BSupermolecules systemsA ……B ….. C Supramolecular C ….. Aassemblies non-covalent bonds (intermolecular) The hierarchy of structural organization of matter Atomsa b c MoleculesA(a-a) B(a-b) C(b-c) covalent bonds Biological Community of mutually dependent functionally different systems supramolecular systems

  41. Formation of Atoms - properties of elementary particles There are elementary particles – Atoms will be Formation of Molecules – properties of Atoms There are Atoms – Molecules will be Formation of Supramolecular Systems - properties of Molecules There are Molecules – Supramolecular Systems will be Formation of Biological Systems – properties of Supramolecular Systems There are Supramolecular Systems – Biological Systems will be LIFE will be!

  42. Life is the form of existence of supramolecular systems Origin of life is predestinated (by corresponding conditions)

  43. A.Lima-de-Faria, Evolution without Selection, Form and Function by Autoevolution ,1988 Biological evolution exists because it was inevitable. At dawn of Universe proton, neutrino and bosonpossessed qualities, which made the following evolution of plants and animals unavoidable. .

  44. E 106ev 10 ev ep a m ss bs? ep a m ss bs 1 ev Arrow of time, evolution, complexity

  45. 1 ev 10 ev + ΔE Socialevolution Pre-biological evolution Biological evolution people a m ss bs 0 - ΔE 106ev

  46. SELF - ORGANIZATION OF STRUCTURES ____________ SELF - ORGANIZATION OF PROCESSES Benar cells Belousov – Jabotincky reaction _____________ I.Prigogine, H.Haken, P.Davies

  47. BENAR CELLS

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