2. Aim of the Lectures
⢠Scope of Biochemistry
⢠Get acquainted with life processes
⢠Know about living organisms
⢠Learn about biomolecules
⢠Know the composition of living
organisms
⢠Learn about the characteristics of
water
5. Two Big Questions
1. What is the manner in which the ancestor
emerged from materials available then?
Can we reconstruct it?
2. How did all extant living organisms evolve
from the common ancestor?
6. The Origin of Life â a Fact and
an Assumption
⢠Unity of life â all extant living organisms
are constructed of the same materials,
and function according to the same
principles .
⢠All organisms are descendants of a
single ancestral form of life.
De duve ,chap1
7. A Problematic Issue in Creating
RNA
⢠Itâs not likely that RNA molecule was created in
prebiotic conditions mainly because of the
difficulty in attaching pyrimidines (C, U) to ribose
to form pyrimidines nucleosides.
A period of time
when
environment
enabled RNA to
be created
Primitive clay
self-replicating
system, from
which an RNA
system evolved
A simpler RNA-like
molecule, maybe
only with purines
(A, G) and from
which an RNA
system evolved
Joyce, 1989
8. Creating Life in the âWarm little Pondâ
Creating the Monomers
Making Polymers
Making Systems
9. 1. Buildup of building blocks in solution.
2. Formation of Coacervates.
3. Heterotrophic.
Problems.
1. Low concentration of building blocks.
2. Hydrolysis favoured.
3. No reasonable pathway to the nucleotides.
4. Chirality.
Oparin-Haldane (late 20s) (from Fenchel, 1998)
10. From Schopf,2002
The Building Blocks â The first experiment
Urey, Miller 1953 â from Schopf, 2002 & Smith, Szathmary,1995
11. Schopf, 2002
1. Early atmosphere probably didnât
contain hydrogen H2. This reduces the
production of organics.
2. Most polymers are unstable at high
temperature. Does not replicate by
themselves reliably, when longer than
40-60 units.
3. A non chiral system cannot select
among mirrored versions of the same
molecule.
Problems
12. Heterotrophic
theory
â˘A primordial soup of simple
molecules arose first
â˘Driven by non biological
energy like radiation or heat
â˘Assembled in complex
molecules and
â˘Led to primitive life forms
14. Colloids and surfacesA: Physicochem Eng. Aspects 2003
219: 281-290.
A comparison of micelle formation of ionic
surfactants in formamide, in N-methylformamide
and in N, N-dimethylformamide.
M.Salim Akhter, Sadeq M. Alawi
Langmuir. 2004 Jan 20;20(2):329-35.
Solvation dynamics of formamide and
N, N-dimethylformamide in aerosol OT reverse micelles.
Shirota H, Segawa H.
âFormamide has a high boiling point, without azeotropic effects, and a wide range of
uses as a solvent. It has an efficient solubilizing effect on nucleobases, nucleosides,
nucleotides, amino acids, proteins, sugars, metalsand saltsâ
Becker, B. J. Chem. Eng. 1970
Formamide.
Phisical and Chemical properties
15. HCN + H2O
H2N H
O
Formamide
+ H2O
-
O H
O
Ammonium formate
NH4
+t1/2= ca. 40 yr
at 60°C and
pH 6.0
t1/2 ca. 10 yr
at 30°C and
pH 6.0
radical
conditions
H H
O
Formaldehyde
Sugars
Thermal
degradation
> 210 °C
HCN H2O
NH3 CO
Thermal
degradation
(Hofmann, Ber.
1882)
HNCO H2
(Lin, Langmuir 1994)
Hydrogen
cyanide
(A) (B)
(C)
(D)
Elemental formamide chemistry
17. The role of minerals and metal oxides on
prebiotic processes. A general overview
⢠Minerals can accumulate the prebiotic
precursors (concentration effect)
⢠Minerals can act as catalytic environments,
reducing the activation energy for the
formation of products
⢠Minerals can tune the selectivity of
prebiotic syntheses
⢠Minerals may act as a template
⢠Minerals are benign environments to
degradation
18. Bioorganic Med. Chem. 9 (2001) 1249-1253
A Possible Prebiotic Synthesis of Purine, Adenine, Cytosine, and 4(3H)-
Pyrimidinone From Formamide: Implications for the Origin of Life
Raffaele Saladino,Claudia Crestini, Giovanna Costanzo, Rodolfo Negri and Ernesto Di Mauro
19. Outline
⢠What Are the Distinctive Properties of Living
Systems?
⢠What Kinds of Molecules Are Biomolecules?
⢠What Is the Structural Organization of Complex
Biomolecules?
⢠How Do the Properties of Biomolecules Reflect Their
Fitness to the Living Condition?
⢠What Is the Organization and Structure of Cells?
⢠What Are Viruses?
20. Essential Question
⢠Despite the spectacular diversity of life, the
elaborate structure of biological molecules, and the
complexity of vital mechanisms, are life functions
ultimately interpretable in chemical terms?
21. Outline
⢠1.1 Distinctive Properties of Living
Systems
⢠1.2 Biomolecules: Molecules of Life
⢠1.3 Biomolecular Hierarchy
⢠1.4 Properties of Biomolecules
⢠1.5 Organization and Structure of Cells
⢠1.6 Viruses as Cell Parasites
22. On Life and Chemistry...
⢠âLiving things are composed of lifeless
moleculesâ (Albert Lehninger)
⢠âChemistry is the logic of biological
phenomenaâ (Garrett and Grisham)
23. Chapter 3 Biomolecules pages 53-73
99% of the mass of most cells is H, O, N, and C
These are the smallest elements that can form 1,2,3 and 4 bonds.
Required in grams/day
Required in milligrams
or less/day
24.
25.
26. 1.1 Distinctive Properties of
Living Systems
⢠Organisms are complicated and highly
organized
⢠Biological structures serve functional purposes
⢠Living systems are actively engaged in energy
transformations
⢠Living systems have a remarkable capacity for
self-replication
27. 1.2 Biomolecules: The
Molecules of Life
H, O, C and N make up 99+% of atoms in the
human body
ELEMENT PERCENTAGE
Oxygen 63
Hydrogen 25.2
Carbon 9.5
Nitrogen 1.4
28. 1.2 Biomolecules: The
Molecules of Life
⢠What property unites H, O, C and N that
renders these atoms so appropriate to the
chemistry of life?
⢠Answer: Their ability to form covalent
bonds by electron-pair sharing.This is
possible due to their capacity to form sp3
hybrids
29.
30.
31.
32.
33.
34. 34
Hierarchical structure of life
⢠The biosphere - Global resource cycles
⢠Biomes - Energy and material interchange
⢠Ecosystems - Species interdependence
⢠Animal populations - Competition and the food chain
⢠Individual organisms - Physiological functioning
⢠Limbs, physiological systems - Organism homeostasis
⢠Tissues - Growth, maintenance, repair
⢠Cells - Growth, specialisation, death
⢠Organelles - Cell homeostasis
⢠Macro Molecules - Folding, recognition, binding
⢠Building Block Molecules - Combine to form polymers
⢠Chemical elements - Chemical binding
35. 1.3 A Biomolecular Hierarchy
Simple Molecules are the Units for Building
Complex Structures
⢠Metabolites and Macromolecules
⢠Organelles
⢠Membranes
⢠The Unit of Life is the Cell
38. 1.4 Properties of Biomolecules Reflect
Their Fitness to the Living Condition
⢠Macromolecules and Their Building Blocks
Have a âSenseâ or Directionality
⢠Macromolecules are Informational
⢠Biomolecules Have Characteristic Three-
Dimensional Architecture
⢠Weak Forces Maintain Biological Structure and
Determine Biomolecular Interactions
39. 1.2 Biomolecules: The
Molecules of Life
What are the bond energies of covalent
bonds?
Bond Energy kJ/mol
H-H 436
C-H 414
C-C 343
C-O 351
40.
41.
42.
43.
44.
45.
46.
47.
48. 1.4 Properties of Biomolecules
Reflect Their Fitness to the
Living Condition
Important numbers!
⢠van der Waals: 0.4-4.0 kJ/mole
⢠Hydrogen bonds: 12-30 kJ/mole
⢠Ionic bonds: 20 kJ/mole
⢠Hydrophobic interactions: <40 kJ/mole
49.
50. Two Important Points About
Weak Forces
⢠Biomolecular Recognition is Mediated by
Weak Chemical Forces
⢠Weak Forces Restrict Organisms to a
Narrow Range of Environmental Conditions
65. Biomolecules are compounds of carbon
Carbon atoms form 4 tetrahedral single bonds.
Two carbon atoms sharing a single bond can
rotate around the single bond.
66. Two carbon atoms sharing a double bond
are closer and cannot rotate about the
double bond. The carbons and the
atoms bound to them form a plane.
70. Functional groups can have chirality
The central carbon (Îą-carbon) is a chiral center
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85. Organization and Structure of
Cells
⢠Prokaryotic cells
â A single (plasma) membrane
â no nucleus or organelles
⢠Eukaryotic cells
â much larger in size than prokaryotes
â 103
-104
times larger!
â Nucleus plus many organelles
â ER, Golgi, mitochondria, etc.
86.
87. ⢠The cell is the smallest unit of
life.
⢠All organisms are composed one
or more cells.
⢠New cells arise from previously
existing cells.
115. Physical and Chemical Properties of Water
Physical and Chemical Properties of Water
High â Boiling point, melting point, heat of
evaporation, surface tension, viscosity, dielectric
constant
Density maximum at 4°C
144. Water is a familiar solvent, but has many
anomalous properties
Ken A. Dill, et al. Modeling water, the hydrophobic effect, and ion solvation.
Ann. Rev. Biophys. Biomol. Struct., 34 : 173-199
Simple models demonstrate how water can be more dense as a
liquid than as ice
145. Water becomes highly organized
around solutes to maximize the
number of hydrogen bonds
Dill et al., 2005
146. Clathrates - Water Reorganization
Crystal structure of diethylamine hydrate
Waters reorient to maintain full H-bonding, even in the presence of non-
polar solutes, forming âcagesâ.
Water molecules become highly organized.
(Each water molecule loses up to 2 entropy units, ~0.6 kcal/mol)
147. Understanding The Hydrophobic Effect
⢠By self-associating, hydrophobic molecules
reduce the amount of non-polar surface exposed to
solvent.
⢠This explains the separation of oil and water.
Restrict oil to one phase, water to another, and
minimize the extent of water reorganization
⢠Association of hydrophobes is the result of an
increase in the disorder of water, not merely due to
âsticking interactionsâ between the hydrophobes
148.
149.
150. Interaction between Non polar and Polar Substances
and Water
Hydrophilic (water-loving) substances (polar and ionic
(electrolytes)) readily dissolve in H2O
Hydrophobic (water-fearing) molecules are nonpolar
Hydrophobic effect - the exclusion of nonpolar
substances by water (critical for protein folding and self-
assembly of biological membranes)
Amphipathic molecules have hydrophobic chains and
ionic or polar ends.
Heterotrophic theory tra le teorie piĂš studiate suggerita per la prima volta in the
Precursori chimici elementari si formano mediante reazioni nellâatmosfera prebiotica si concentrano nella prebiotic soup dove avvengono trasformazioni piĂš complesse fino
Formata da ossidi per scarica elettrica o da hcn idrolisi che è uno dei precursori chimici
La reattività della formammide può essere tunata da metalli e ossidi metallici
Sintetizzate contemporaneamente
2. Have Mars been checked for chirality?
3. How far away can chirality be observed?
2 centrioles, nine clusters of microtubule triplets
FIGURE 2.1 The structure of water. Oxygen has a partial negative charge, and the hydrogens have a partial positive charge. The uneven distribution of charge gives rise to the large dipole moment of water. The dipole moment in this figure points in the direction from negative to positive, the convention used by physicists and physical chemists; organic chemists draw it pointing in the opposite direction.
FIGURE 2.6 A comparison of linear and nonlinear hydrogen bonds. Nonlinear bonds are weaker than bonds in which all three atoms lie in a straight line.
FIGURE 2.3 Ionâdipole and dipoleâdipole interactions help ionic and polar compounds dissolve in water. (a) Ionâdipole interactions with water. (b) Dipoleâdipole interactions of polar compounds with water. The examples shown here are an alcohol (ROH) and a ketone (R2CAO).
FIGURE 2.2 Hydration shells surrounding ions in solution. Unlike charges attract. The partial negative charge of water is attracted to positively charged ions. Likewise, the partial positive charge on the other end of the water molecule is attracted to negatively charged ions.
FIGURE 2.5 Micelle formation by amphipathic molecules in aqueous solution. When micelles form, the ionized polar groups are in contact with the water, and the nonpolar parts of the molecule are protected from contact with the water.
FIGURE 2.4 An amphiphilic molecule: sodium palmitate. Amphiphilic molecules are frequently symbolized by a ball and zigzag line structure, where the ball represents the hydrophilic polar head and the zigzag line represents the nonpolar hydrophobic hydrocarbon tail.
FIGURE 2.10 The ionization of water.
FIGURE 2.12 pH versus enzymatic activity. Pepsin, trypsin, and lysozyme all have steep pH optimum curves. Pepsin has maximum activity under very acidic conditions, as would be expected for a digestive enzyme that is found in the stomach. Lysozyme has its maximum activity near pH 5, while trypsin is most active near pH 6.
FIGURE 2.13 Titration curve for acetic acid. Note that there is a region near the pKa at which the titration curve is relatively flat. In other words, the pH changes very little as base is added in this region of the titration curve.
FIGURE 2.14 Buffering. Acid is added to the two beakers on the left. The pH of unbuffered H2O drops dramatically while that of the buffer remains stable. Base is added to the two beakers on the right. The pH of the unbuffered water rises drastically while that of the buffer remains stable.
FIGURE 2.15 The relationship between the titration curve and buffering action in H2PO4 -. (a) The titration curve of H2PO4 -, showing the buffer region for the H2PO4 -/HPO4 2- pair.
FIGURE 2.16 Two ways of looking at buffers. In the titration curve, we see that the pH varies only slightly near the region in which [HA] = [A-]. In the circle of buffers, we see that adding OH- to the buffer converts HA to A-. Adding H+ converts A- to HA.
FIGURE 2.16 Two ways of looking at buffers. In the titration curve, we see that the pH varies only slightly near the region in which [HA] = [A-]. In the circle of buffers, we see that adding OH- to the buffer converts HA to A-. Adding H+ converts A- to HA.