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Chapter 2: Biomolecules in Water 水做為溶劑之特殊性 非共價作用力 解離常數與 pH 緩衝溶液
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水為生物的首選溶劑 Biological solvent: a medium for metabolic reactions – –aquaporins: membrane channels for water transport Essential buffer to regulate temperature and pH: high specific heat capacity and pH-regulating substances dissolved in it Participant in many biochemical reactions: photosynthesis and hydrolysis of ATP
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水是威力強大的小分子
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Weak Chemical Bonds Non-covalent interactions: – Hydrogen bonds 氫鍵 – Ionic interactions 離子交互作用 ( 靜電吸引力 ) – Hydrophobic interactions ( 厭水性交互作用 ) – van der Waals interactions ( 凡得瓦爾力 ) 這些弱的維繫力重要性何在 ? *
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“The more complex the system, the weaker are the forces that govern its behavior” - J. R. Platt 較強 較弱 Forces: 核間力原子力 共價鍵 非共價鍵 重力 _________________________________________ Structure: 原子核原子 簡單化合物 生物巨分子 宇宙 簡單 複雜
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The Four Weak Interactions * 共通特質: 1. 非共價 2. 可逆 3. 專一
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The Polar Nature of Water Given the difference in electronegativity between oxygen and hydrogen (3.5 - 2.1 = 1.4) and its shape, water is a polar molecule with a dipole moment of 1.85D –the net charge on oxygen is -0.66 and that on each hydrogen is +0.33
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1. Hydrogen Bonds < 5% of the bond strength of a O-H (20 vs. 460 kJ/mole) Much longer bond distance: 0.18 vs. 0.096 nm Highly directional Based on the dipole moment of water Account for the unusual properties of water as both substance and solvent
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Common Hydrogen Bonds * Peptides X-H:::A X= Hydrogen bond donor N, O, S A= Hydrogen bond acceptor O, N
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Hydrogen bonding in ice 冰為何浮 在水上? Ice crystal: static Water: dynamic breaking and forming
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重要生物分子間氫鍵
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Hydrogen Bond Strength is Highly Directional Fig. 2-5
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2. Ionic Interactions 2. Ionic Interactions They are about 5-10% the strength of a carbon-carbon bond (20-40 vs. 350 kJ/mole) Ionically stabilized compounds (like NaCl) are readily dissolved in solvents with a high dielectric constant (like water) Why? F= Q 1 Q 2 / r 2 : dielectric constant r: distance between the charge groups
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Solvent Properties of H 2 O Ionic compounds (e.g.,KCl) and low- molecular- weight polar covalent compounds (e.g., C 2 H 5 OH and CH 3 COCH 3 ) tend to dissolve in water The underlying principle is electrostatic attraction of unlike charges; the positive dipole of water for the negative dipole of another molecule, etc. –ion-dipole interaction: e.g., KCl dissolved in H 2 O –dipole-dipole interactions: e.g., ethanol or acetone dissolved in H 2 O –dipole induced-dipole interactions: weak and generally do not lead to solubility in water
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Dipole-Dipole Ion-Dipole
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Salts Dissolve in Aqueous “Cages of Hydration” Fig. 2-6 還有什麼因素讓鹽很容易溶於水?
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氧既是非極性,又如何支持生命?
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3. Hydrophobic Interactions They are about 2% the strength of a carbon- carbon bond (8 vs. 350 kJ/mole) Water becomes highly ordered around hydrophobic groups Greasy chains stay together to minimize entropy loss by water
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水的退出有利酵素與受質作用
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4. van der Waals Interactions They are about 1% the strength of a carbon-carbon bond (4 vs. 350 kJ/mole) Attraction between atoms by transiently- induced dipoles Repulsion when the electron clouds bump together
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