ON WATER IN EXTREMELY DRY BIOLOGICAL SYSTEMS HUBERT HARANCZYK ON WATER IN EXTREMELY DRY RIOLOGICAL SYSTEMS WYDAWNICTWO UNIWERSYTETU JAGIELLOŃSKIEGO Rozprawy Habilitacyjne Uniwersytetu Jagiellońskiego Nr 361 Publikacja finansowana przez Instytut Fizyki Uniwersytetu Jagiellońskiego RECENZENT Jerzy S. Blicharski PROJEKT OKŁADKI Dorota Heliasz REDAKCJA Jerzy Hrycyk © Copyright by Hubert Harańczyk & Uniwersytet Jagielloński All rights reserved Wydanie I, Kraków 2003 ISBN 83-233-1713-5 1SSN 0239-782X Wydawnictwo Uniwersytetu Jagiellońskiego Dystrybucja: ul. Bydgoska 19 C, 30-056 Kraków tel. (012) 638-77-83, fax: (012) 636-80-00 w. 2023, (012) 430-19-95 tel. kom. 0604 414-568, e-mail: wydaw@if. uj. edu.pl Konto BPH BPK SA IV/O Kraków nr 10601389-320000478769 www.wuj. pl Contents 0. Preface .................................................................................................................. 11 1. Water properties, its role in biological systems Preface......................... 15 1. 1 Water molecule............................................................................................. 15 1.2 Macroscopic anomalies of water .............................................................. 16 1. 3 Hydrogen bond............................................................................................. 17 1.4 Ordinary ice (Ih)........................................................................................... 20 1. 5 Ice polymorphs ............................................................................................. 21 1. 6 Freezing of water......................................................................................... 23 1. 7 Hydrogen bonds in Mendeleevian neighbors of oxygen....................... 24 1. 8 Liquid water ................................................................................................. 25 1.9 Self-diffusion of water................................................................................. 27 1. 10 Water dissociation and ion migration..................................................... 27 1.11 Layering of water in restricted space...................................................... 29 1. 12 Supercooling of water................................................................................ 29 1.12. 1 Freezing of supercooled water ....................................................... 30 1. 12.2 Comparison with other liquids ....................................................... 31 1. 12. 3 Properties of supercooled water ..................................................... 32 1.12. 3. 1 Density and expansivity............................................................. 32 1.12. 3. 2 Isothermal compressibility........................................................ 32 1. 12. 3. 3 Heat capacity ............................................................................... 33 1.12. 3. 4 Diffusion coefficient, viscosity................................................. 33 1. 12. 4 Singularity in supercooled water.................................................... 33 1. 13 Wetting of surfaces.................................................................................... 34 1.13. 1 Young condition................................................................................ 34 1. 13. 2 Core region........................................................................................ 35 1. 13. 3 Breath figures .................................................................................... 36 1. 13. 4 Water clustering on glass surface................................................... 37 1. 14 Hydrophobic effect.................................................................................... 41 1. 14. 1 Solubility of hydrocarbons .............................................................. 42 1. 14.2 Solubility of amphiphiles ................................................................ 45 6 Contents 1. 14. 3 Molecular picture of hydrophobic effect....................................... 46 1.15 Micelles ....................................................................................................... 47 1. 16 Monolayers................................................................................................. 50 1.17 Lipid bilayer ............................................................................................... 52 1. 18 Lipid phase polymorphism ....................................................................... 56 1. 19 Bound water ............................................................................................... 58 1.20 Biological membrane................................................................................ 61 1.21 Phase transitions in photosynthetic membranes ................................... 64 1. 21.1 Gel-to-liquid crystalline phase transitions in photosynthetic membranes.................................................................................................... 64 1. 21.2 Phase transition at inactivation of photosynthetic membrane.... 66 1.21. 3 Non-lamellar phases in photosynthetic membrane lipids........... 66 1.21. 4 Non-lamellar phases in photosynthetic membranes .................... 67 1. 21.4. 1 Non-lamellar phases in native photosynthetic membranes... 68 1.21. 4. 2 Glycerol effect on the non-lamellar phase formation in photosynthetic membrane......................................................................... 70 1.21. 4. 3 Non-lamellar phases in photosynthetic membranes reconstituted after lyophilization..................................................................................... 71 1.21. 4. 4 Glycerol effect of non-lamellar phases in photosynthetic membranes reconstituted after lyophilization........................................ 74 1.21. 5 Denaturation of temperature-resistant membrane proteins......... 75 2. Nuclear magnetic resonance applied to dry biological systems........... 77 2. 1. Elements of nuclear magnetic relaxation................................................. 77 2.1. 1. The dynamics and relaxation of nuclear spin systems ................. 77 2.1. 2 Diffusion equation.............................................................................. 82 2.1. 2.1 Selfdiffusion .................................................................................. 83 2.1. 2. 1. 1 Translationaiselfdiffusion..................................................... 84 2.1. 2. 1. 2 Rotational selfdiffusion......................................................... 84 2.1. 3 Correlation times ................................................................................ 85 2.1. 4 Chemical shift...................................................................................... 85 2.1. 5. Why not NMR-tomography? .......................................................... 86 2. 2. NMR relaxation function analysis............................................................ 87 2. 2. 1. Stretched exponential (SE) and modified stretched exponential (MSE) function.............................................................................................. 88 2. 2. 2. Spin-grouping technique .................................................................. 91 2.2. 3. Functions fitted to the relaxation data ............................................ 92 2.2. 4. Non-linear least squares fitting........................................................ 92 2.2. 5. The selection of sampling times...................................................... 93 2. 2. 6. Selection of the best-fitted model.................................................... 93 2.2. 7 Computer program CracSpin............................................................. 94 2.2. 7. 1. One-dimensional data analysis .................................................. 95 2.2. 7. 1. 1. Effect of S/N and overparamerization of model .............. 95 2.2. 7. 1. 2. Effect of baseline and sampling range ............................... 96 Contents 7 2.2. 7. 1. 3. Resolution limits for time constants.................................... 97 2.2. 7.2. Two dimensional data analysis ................................................ 99 2.3 Multiexponential or SE relaxation function in pores of dry biological system? ................................................................................................................. 101 2.3. 1 Analysis of simulated data ................................................................ 101 2. 3.2 SE versus multiexponential fits of data for porous rocks............. 102 2. 4 Paramagnetic ion behavior in wet porous silica glass ............................ 106 2.5. Water soluble solid fraction in dry biological system (bast and seed) 114 2.5. 1 Bark and bast composition ................................................................ 114 2. 5. 1. 1 Polysaccharides............................................................................. 115 2.5. 1. 2 Suberins ......................................................................................... 117 2.5. 1. 3 Lignin.............................................................................................. 117 2.5. 1.4 Extractive components................................................................. 117 2. 5. 1.5. Mineral components ................................................................... 118 2.5. 2 Bark and bast structure ....................................................................... 118 2.5. 2. 1 Cell wall........................................................................................