Medical Biochemistry pH

Objectives of pH Lectures encompass three areas of Biochemistry
1  Details of Chemical/Equilibrium: Foundation of pH Balance & Regulation –  Understanding of pH = -log[H+] –  Know the Behavior of Weak Acids and Bases
•  Proton donors & acceptors

–  Be able to use the Henderson-Hasselbach Eq.
•  pH = pK + log(conjugate base/conjugate acid)

–  Role of Buffers in pH Balance & Regulation

Objectives of pH Lectures encompass three areas of Biochemistry
2  Role of pH in Macromolecular Structure and Enzyme Mechanism & Regulation
–  Relationship between Amino Acid Side Chain, Structure & Catalytic Groups –  Role of pH in Protein Structure and Catalytic Mechanism –  Acid-Base Catalysis – H+ donor - acceptor –  Regulation of Hemoglobin •  Bohr Effect (T → R) •  O2 Transport (linkage to CO2 transport)

Na+.+ H+ . NH4+ –  Mitochondria & ATP synthesis –  Transport and Effectiveness of Drugs (M2’s) •  DH ↔ D.Kidney Function •  HCO3-. K+. H2PO4-.Lung Function •  O2 and CO2 transport –  Metabolic control . H2CO3.Objectives of pH Lectures encompass three areas of Biochemistry 3  Role of pH in Physiology & Pharmacology –  pH Balance in Respiration control .

Water •  •  •  •  •  70% of your Body Net Dipole tetrahedral electronic structure H-bonds between 4 nearest neighbors good solvent properties –  high boiling point. heat of vaporization –  hydrophobic effect .

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Solvent Properties of Water •  Polar molecules readily disperse in H2O •  Salts dissolve in a shell of H2O dipoles •  Amphipathic molecules contain polar & nonpolar groups •  Hydrophobics do not disperse & form micelles •  Electrolytes dissociate into anions & cations –  NaCl. sugars & alcohols . KCl. NaOH •  Weak Electrolytes partially dissociate •  Nonelectrolytes dissolve but do not dissociate eg. strong acids & bases HCl.

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ACID + BASE <-> Conjugate ACID + Conjugate BASE HA + H2O <-> H3O+ <-> H3O+ <-> H3O+ + + + AClOH- HCl + H2O H2O + H2O ELECTROLYTES .

Water is a Weak Electrolyte HOH <=> H+ + OHKeq = 1.0 x 10-14 = Kw pKw = -logKw = 14 .8 x 10-16 = [H+] [OH-] / [H2O] Keq x [H2O] = [H+] [OH-] = Kw Keq x 55.5 M = 1.

1 M HA if Keq = 1.+ H+ Keq = [H+] [A-] / [HA] [ ] = moles/liter Do problem: 0.38 x 10-4 .Weak Electrolytes Partially Dissociate •  eg: Lactic acid •  CH3-CHOH-COOH <=> CH3-CHOH-COO.

0 x 10-7 or pH = pOH = 7.Water is a Weak Electrolyte pH = log 1 / [H+] = -log [H+] in pure water [H+] = [OH-] thus [H+] = [OH-] = 1.0 pKw = pH + pOH = 14 .

Kw = [H+] [OH-] = constant = 1.0 x 10-14 pKw = pH + pOH = constant = 14 .

(40 nM) .

is an acid or a base •  (H2PO4.Weak Acids & Bases •  Acid is a proton donor •  Base is a proton acceptor •  Weak acids dissociate into a conjugate acidconjugate base pair (pK = -logK) –  eg.+ H+ <=> H3PO4) •  (H2PO4.+ H+ –  H3PO4 is an acid (H3PO4 <=> H2PO4.+ H+) –  PO4-3 is a base (PO4-3 + H+ <=> HPO4-2 ) –  H2PO4. Lactic acid <=> Lactate.<=> HPO4-2 + H+) .

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Henderson-Hasselbalch Equation Conjugate acid <=> Conjugate base + H+ Keq = [H+] [base] / [acid] {1/[H+]} = {1/ Keq} x [base] / [acid] log{1 / [H+]} = log{1/ Keq} + log [base] / [acid] pH = pK + log [base] / [acid] .

8? pH = 5.8? .Why is this the buffering region? pH = 3.

7 .D Fig 1.

pH = pK + log(B/A) D Fig 1.6 .

8 .D Fig 1.

.Amino acids are zwitterions with multiple groups that can lose protons and act as buffers.

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(aq) H+ + HCO3 .BICARBONATE and CO2 NaHCO3 (s) <-> Na+ (aq) + CO2 + HCO3 .<-> H2O Acid Base Buffering Soda If carbonate ion is present in blood and there is a source of H+ added it will be buffered and form H2O + CO2 .

H+(aq) + A-(aq) -> HA(aq) Any added OH.BUFFERS The solution contains a weak acid HA and its conjugate base A-. Any added H+ reacts with the base A-. The buffer resists changes in pH by reacting with any added H+ or OH. OH-(aq) + HA(aq) -> H2O(l) + A-(aq) .reacts with the weak acid HA.so that these ions do not accumulate.

4 how much DH (10 mM. pK 6) is uncharged if DH ↔ D.! At pH 7.+ H+ ? .

•  Assignment: Do Quiz 1 on blackboard ! •  M1’s use BICH 610 Biochemistry section 1 2012-2013 FALL •  G1’s use Graduate Biochemistry (BCH 710) .

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