Chem 431A-L28-F’07 page 1 of 2 Chem 431A-L28-F’07 wednesday admin: Inclass Quiz 10 . Online quiz9 deadline is Monday (Chapt 11). In class quiz is Friday (membranes, transport) Review guide for final (65pts) posted today Last time: transport thermodynamics Today: problem solving + review (ask me how you are doing) Fri: talk + survey + quiz Last time: For a solution: G = RTlnC so ∆G between 2 sides of memb: final – initial ∆G = Gf –Gi =RTlnCf-RTln Ci = RTln(Cf/Ci) C1 C2 Simple diffusion case. Lipid bilayer membrane (H2O diffuses easily!) 3 kinds of diffusion-driven transport Process: C1 C2 net charge transport 2 different aspects: rate (kinetics) & spontaneity(thermodynamics) J=-P(C2-C1) (1)∆G= RTln(Cf/Ci) (2)∆G= RTln(Cf/Ci) +ZF∆Y (3)∆G= RTln(Cf/Ci) + ∆G’ permeability(deps on S solubility in memb.) coupled chem rxns Kinds of transporters: simple (nonmediated) facilitated Uniport (mediated) Cotransporters: (transporters,permeases) Symport ∆G’=0, “passive” carrier channel(pore) slow fast very fast Antiport factors to distinguish speed, specificity saturatable or not? Competitive? Can be inactivated? Symports and antiports are obligatory. Transporters are not really enzymes but function similarly (lower activation energy, can be inactivated or modified) primary Active transport: coupled reactions usu. to ATP hydrolysis. [A]low ATP [A]high ADP+Pi secondary [B]high [B]low [A]low [A]high ATP [B]high [B]low ADP+Pi In secondary active transport, the transport of A is by symport driven by B gradient kept high by another active transport mechanism Chem 431A-L28-F’07 page 2 of 2 Problem solving practice: Problem solving practice: Consider: note: T = 298, R = 8.314 J/mol K , 1 C-V = 1 joule; ∆G = 2.303RTlogC2/C1 + ZF∆Ψ +∆G’ 1) A neutral solute crosses a membrane by passive ∆G=RT lnC2/C1 = diffusion. If its concentration is 1 mM on the left (8.314J/molK)(298K)ln(100/1)=+11,400 J/mol = side and 100 mM on the right side, what is the free +11.4 kJ/mol (non spontaneous) energy change for the transport of 1 mole of solute from left to right? 2) K+ ions cross a membrane from inside (140mM ∆G=RT lnC2/C1 + ZF(Ψ2 - Ψ 1) = K+) to outside (4mM K+) by facilitated diffusion (via a pore). The membrane potential is 100 mV (+ (8.314J/molK)(298K)ln(4/140)+(+1)(96500)(.1V) =-8.81 kJ/mol +9.65 kJ/mol = +0.84 kJ/mol on the right side of the membrane). Is the process (nonspont) of crossing from inside to outside spontaneous? 3) Consider the Na+/K+ -ATPase transport system. ∆G=2 RT ln{[K+]i/[K+]o}+ 3 RT ln{[Na+]o/[Na+]i} For every ATP hydrolyzed, 3 Na+ ions move out of + 2(+1)(96500C/mol)(-0.070V) + the cell and 2 K ions move into the cell. The +3(+1)(96500C/mol)(+.070V)+(-30.5kJ/mol) membrane potential is -70 mV (that is, - on the = +12.2 kJ (non spontaneous at std conditions of inside and + on the outside ). The standing ATP and ADP and Pi. They must be at non std + concentrations of the relevant ions are: [K ]out = + + + conditions in the cell to make the ∆G’ for ATP 4mM, [K ]in = 140 mM, [Na ]out = 145mM, [Na ]in hydrolysis to be negative enough to allow for the = 12mM. Note also: ion pumping. ATP +H2O ADP + HPO +H ∆G’= -30.5 4- 3- 24 + kJ/mol Recall: ∆G’ = ∆G°’+RTlnQ What is ∆G’ for this transport? (assume pH =7) where Q = [ADP][Pi]/[ATP] Resting membrane potential ∆Ψ of a cell: Consider: ∆G = RT ln (C2/C1) + ZF∆Ψ at equilibrium (assuming only passive diffusion) ∆G =0 = RT ln(C2/C1) + ZF∆Ψ solve for ∆Y: ∆Ψ = -(RT/ZF)ln(C2/C1) “Nernst Equation” magnitude: ∆Ψ= -2.303(RT/ZF)log(C2/C1) = (60mV/Z) log(C2/C1) let’s draw it. For example, [K]1 = 10mM. [K]2=1mM what is the resting potential? For example: pH1 = 2, pH2 =10 , what is ∆Ψ? For K+ example: ∆Ψ= -2.303(RT/ZF)log(C2/C1) = (60mV/Z) log(C2/C1) =60mV(log(1/10)= -60 mV it must be + in the side that’s low in [K+] for the system to be at equilibrium. pH example: ∆Ψ= -2.303(RT/ZF)log(C2/C1) = -2.303(RT/ZF)log([H+]2/[H+]1) =60mVpH1-pH2 = 60mV (∆pH) =60mV(10-2)=480mV .+ on the high pH side

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