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'"  )!# ! #'"%*(*r$SL Ei 2$E3)6b4:4i R$bB!/Mp' R$p-xϧņpdL r$`nxּfaid r$g\Oy Ekid 2$d_qdhe 2$&eRuw%g 2$ƞگAnjdSw 2$KU9~D뒈hT ] $ 2$nj-e4YJ)Vg  0e0e     A@ A5% 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||S" 33333f@8{̊ ʚ;2Nʚ;g4JdJd0p@p<4!d!d 0LT:<4dddd 0LT: <4BdBd. 0L? %!*5Review of Analytical Methods Part 2: Electrochemistry66Roger L. Bertholf, Ph.D. Associate Professor of Pathology Chief of Clinical Chemistry & Toxicology University of Florida Health Science Center/Jacksonville  -Analytical methods used in clinical chemistryaSpectrophotometry Electrochemistry Immunochemistry Other Osmometry Chromatography Electrophoresis:9)),# Electrochemistry Electrochemistry applies to the movement of electrons from one compound to another The donor of electrons is oxidized The recipient of electrons is reduced The direction of flow of electrons from one compound to another is determined by the electrochemical potentialnSIoCUElectrochemical potentialoFactors that affect electrochemical potential: Distance/shielding from nucleus Filled/partially filled orbitals&/A/ARelative potentialCopper is more electronegative than Zinc When the two metals are connected electrically, current (electrons) will flow spontaneously from Zinc to Copper Zinc is oxidized; Copper is reduced Zinc is the anode; Copper is the cathodeM{   The Nernst Equation  Electromotive force 3Would the reaction occur in the opposite direction? 2How do we determine standard electrode potentials?Absolute potential cannot be measured only the relative potential can be measured Standard electrode potentials are measured relative to a Reference Electrode A Reference Electrode should be. . . Easy to manufacture StableT & S% The Hydrogen Electrode The Calomel Electrode$The Silver/Silver Chloride ElectrodeIon-selective ElectrodesTypical ISE designActivity and concentrationISEs do not measure the concentration of an analyte, they measure its activity. Ionic activity has a specific thermodynamic definition, but for most purposes, it can be regarded as the concentration of free ion in solution. The activity of an ion is the concentration times the activity coefficient, usually designated by g: P !zH$'The activity coefficientSolutions (and gases) in which none of the components interact are called ideal, and have specific, predictable properties Deviations from ideal behavior account for the difference between concentration and activity Dilute solutions exhibit nearly ideal behavior (g1)6 J Types of ISE&Glass Various combinations of SiO2 with metal oxides Solid-state Involve ionic reaction with a crystalline (or crystal doped) membrane (example: Cl-/AgCl) Liquid ion-exchange A carrier compound is dissolved in an inert matrix Gas sensors Usually a combination of ISE and gas-permeable membrane/ [3 8  S *  8, pH electrodepCO2 electrode$  NH3 electrode$ Other glass electrodesGlass electrodes are used to measure Na+ There is some degree of cross-reactivity between H+ and Na+ There are glass electrodes for K+ and NH4+, but these are less useful than other electrode types )<b'2 88The Sodium Error (or, direct vs. indirect potentiometry)* 8The Sodium Error (or, direct vs. indirect potentiometry)* So which is better?Direct potentiometry gives the true, physiologically active sodium concentration. However, the reference method for sodium is atomic emission, which measures the total concentration, not the activity, and indirect potentiometry methods are calibrated to agree with AE. So, to avoid confusion, direct potentiometric methods ordinarily adjust the result to agree with indirect potentiometric (or AE) methods.>H*PH<RThen what s the  sodium error all about?>When a specimen contains very large amounts of lipid or protein, the dilutional error in indirect potentiometric methods can become significant. Hyperlipidemia and hyperproteinemia can result in a pseudo-hyponatremia by indirect potentiometry. Direct potentiometry will reveal the true sodium concentration (activity).&?ZgE     6 Sodium error'But. . .why does it only affect sodium?RIt doesn t only affect sodium. It effects any exclusively aqueous component of blood. The error is more apparent for sodium because the physiological range is so narrow.Solid state chloride electrodeAgCl and Ag2S are pressed into a pellet that forms the liquid junction (ISE membrane) Cl- ions diffuse into vacancies in the crystal lattice, and change the membrane conductivity6 LZ$R[ "Liquid/polymer membrane electrodesTypically involves an ionophore dissolved in a water-insoluble, viscous solvent Sometimes called ion-exchange membrane electrodes The ionophore determines the specificity of the electrode$ , f ,K+ ion-selective electrode$!Ca++ ion selective electrode$"Ca++ ion selective electrode$% Amperometry "Whereas potentiometric methods measure electrochemical potential, amperometric methods measure the flow of electrical current Potential (or voltage) is the driving force behind current flow Current is the amount of electrical flow (electrons) produced in response to an electrical potentialR#7 67],+ # Amperometry $ Amperometry &Oxygen (pO2) electrode$  '"Reaction at the platinum electrodeEThe amount of current (e-) is proportional to the concentration of O2@F+(The glucose electrodeANote that the platinum electrode now carries a positive potential$B/ \  ` ̙33` ` ff3333f` 333MMM` f` f` 3>?" dd@,|?" dd@   " @ ` n?" dd@   @@``PT    @ ` `p>> z0(    <w ?"`  T Click to edit Master title style! !B  Nz 11ȜȜ?"   RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  0x "``  ^*   0섺 "`   `*   0 "`   `* *  A޽h ?\\Dave-1\Dave-1_D\Graphics Stuff\CrystalGraphic_Templates\Template_083\JPEG-1280x1024\Template_083B.jpg ̙33 (PowerPlugs BGs 2 P06s  #0(    < ?"`  T Click to edit Master title style! !  6  ?"0   W#Click to edit Master subtitle style$ $  0 "``  ^*   0 "`   `*   0 "`   `* *  A޽h ?\\Dave-1\Dave-1_D\Graphics Stuff\CrystalGraphic_Templates\Template_083\JPEG-1280x1024\Template_083A.jpg ̙33 0 z(    0 P    R*     0<     T*   d  c $ ?    0  @  RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  6 `P   R*     6  `   T*   H  0޽h ? ̙33H l(  l l 0 P    Z*   l 0     \*   l 6 `P   Z*   l 6h `   \*  H l 0޽h ? ̙33  0(  x  c $00  x  c $ P   H  0޽h ? ̙33  @$*(  $x $ c $    r $ S t  H $ 0޽h ? ̙33  Ph*(  hx h c $ `   r h S   H h 0޽h ? ̙33   D < `l (  l2 l 0f @ ,$D 02 l 03h ,$D 0x l c $8`    l S p 0<$  0  l 0   l ,$D 02 l ZXd @` ` 2  l Zfd @  0 2 l ZXd @  ` 2 l Zfd @ 0 2 l ZXd @ P 2 l ZXd @ 2 l ZXd @`  0 2  l Zfd @ ` P 2  l Zfd @0 2  l Zfd @ P 0 2  l Zfd @  ` 2 l 0 ,$D 0H l 0޽h ? ̙33`  pt(  t2 t  `7ǵvd @@ <Zn (2 t  `Hvd @ <Cu (2 t  `vd @ p  Le-. j  t Bv @@ 0Pp  t@ HH_v @P x t c $``   r t S    H t 0޽h ? ̙33: .T|@b(  |8 `  B|` x $| Hv2 @`<` $ x2 %| Hv2 @` ` ` &| 0GP ` '| 0G N pph (| `P` ` )| 0p8p `2 *| 0pphf2 +| 6jJpp` ,| 0G0~2 -| Nv2 @>`` ` .| 0G`~2 /| Nv2 @>`` ` 0| 0Gx 1| Hv2 @ <$ x2 2| Hv2 @  ` 3| 0GppP ` 4| 0Gpp N pph 5|  P ` 6| 0p8p `2 7| 0pphf2 8| 6jJpp` 9| 0Gp0p~2 :| Nv2 @> ` ;| 0Gpp`~2 <| Nv2 @> ` =| 0Gpp >| <p ?  ^Cu2+>      | <p q  ^Zn2+>     ?| <xOPm ]Zn0>     @| <Һm ]Cu0>     A| B CDEFԔ  @9`l 0 P  F| 0 ) ,$D  0|2 D| LA Wave0 P |2 E| LA Wave P | C| LA Wave` P x G| < ,$D  0  Zn0 Zn2+ + 2e- d H| < m,$D  0  Cu2+ + 2e- Cu0  I| <9pKY,$D  0 &e- e- e-  f ffff ffff fffl  `  T| ` ,$D 0lr K| <Ԕ ` 2T 0` Q|# -@  `2 O| 00@fB P| 6Do``` R| Bx+   4mV H | 0޽h ? ̙33  ,(  R  s * x  c $p/`   `  c $A ??0o   </ R FRWhere E = Potential at temperature T E0 = Standard electrode potential (25C, 1.0M) R = Ideal gas constant F = Faraday s constant n = number of electrons transferred  #$$$"H  0޽h ? ̙33C 07(  F `   ` x  Hv2 @`<` $ x2  Hv2 @` ` `  0GP `  0G N pph  `P` `  0p8p `2   0pphf2   6jJpp`   0G0~2   Nv2 @>`` `   0G`~2  Nv2 @>`` `  0Gx  Hv2 @ <$ x2  Hv2 @  `  0GppP `  0Gpp N pph   P `  0p8p `2  0pphf2  6jJpp`  0Gp0p~2  Nv2 @> `  0Gpp`~2  Nv2 @> `  0Gpp  <Dp ?  ^Cu2+>      <`Ip q  ^Zn2+>      <FOPm ]Zn0>       <dRm ]Cu0>     !  B CDEFԔ  @`z 0 P  " P 0 ,$D  0|2 # LA Wave0 P |2 $ LA Wave P | % LA Wave` P  & <W  ,$D  0 @DZn0 Zn2+ + 2e- E0 = +(-)0.7628 V#  ' <$d m ,$D  0 ,>Cu2+ + 2e- Cu0 E0 = +0.3402 V   8 `  1 ` lr / <o`   0 <p i ,$D  0 eEljF z  `  2  ` @,$D 0fr 3 6Ԕ ` &T 0` 4# -@  Z2 5 s *0@`B 6 0Do``` 7 <u   4mV H  0޽h ? ̙33  A(  x  c $y    K  <z@% Ecell = Ecathode + Elj - Eanode $$$$$$$$$x  <f4 LEcell = ECu(II),Cu + Elj  EZn(II),Zn' $$$ $$$$ $$V  < !  BEcell = (+)0.340 + Elj  (-)0.763" $$$$$$$ $  <H rRH  Ecell = (+)1.103 + Elj| $$$$$$$6  <0 o DG = -nFEcellr $$$$$$H  0޽h ? ̙33  =(  ~  s *d    K  <R Ecell = Ecathode + Elj - Eanode $$$$$$$$$  <rN  JNEcell = EZn(II)Zn + Elj  ECu(II) Cu( $$$$$$$$$$$$L  0   DEcell = (-)0.763 + Elj  (+)0.340 # $$$ $$$$ $  <X F Ecell = (-)1.103 + Elj| $$$$$$$H  0޽h ? ̙33  *(  x  c $P    r  S `  H  0޽h ? ̙33  (-:(  x  c $<`   l  @  P ,$D 0x2  Hv2 @ @ x  Hv2 @  ~2  Nv2 @Ԕ l     ,$D 0r2   Bv @ r  Bv @  x2   Hv @o Pl p  p ,$D  0f   6G p    B0CDE Fo0@@p p   <`$,$D  0 xH2 gas L  l     P,$D  0ZB  s *DoP @ ZB  s *DoP f2  6o @ 0 P f2  63fop f  6G@ZB  s *D)   <X3fP  ,$D 0 (22H+ + 2e- H2 E0 = 0.0 V xl p Z #p Z,$D  0  `   p  @,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```   <   4mV `B ! 0Do   " <P:Z BTest electrode l 0   - 0 ,$D 0Z2 $ s *MMMP`  @ 0   +0  2 % Zvd @` @ 2 & Zvd @p  2 ' Zvd @0p  2 ( Zvd @ ` 2 ) Zvd @00  2 * Zvd @  H  0޽h ? ̙33  vn#0 (  r  S 0   *8 BPb  "PBb 6@  @0  r@    RA oWave  \T @  #  @0 x  H3v2 @@ @x2  H3v2 @   B@CDE FԔ@@"Pb 0 f   6G___20  ~  N)))v2 @B bl  Q #Q ,$D  0  <$2 Qq  Calomel paste (Hg0/Hg2Cl2)f    `B B 0DԔ" p   <l G g  c Saturated KCl  `B  0DԔ2 2  < R i CLiquid junction `B B 0DԔ`R xl b 0 !0b ,$D  0  `   b 0,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  <   4mV `B  0DԔPRP  <<L BTest electrode $   <T@ P ,$D  0 LHg2Cl2 + 2e- 2Hg0 + 2Cl- E0 = 0.268V'  H  0޽h ? ̙33q  !0 (  r  S '0   <L  @0  # @r |  LA oWave  \T @  #  @0 x  H3v2 @@ @x2  H3v2 @ gl P  P ,$D  0    B@CDE FԔ@@Pb    B+2 Q q  ? Silver wire  fB B 6DԔ" p l ?Z i Z ?i,$D  0  B?Z `  Saturated KCl + AgNO34   fB  6DԔ2 2  B3R i CLiquid junction fB B 6DԔ`R v   N)))v2 @B z b 0  0b ,$D  0  `   b 0,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  <9   4mV `B  0DԔPRP  <|=L BTest electrode   <DA@ y ,$D  0 fDAgCl + e- Ag0 + Cl- E0 = 0.222V#  $H  0޽h ? ̙33Z   +3(  r  S XD`0   v  Nv2 @`` v2  Nv2 @h`` ^  6Gp  ^  6G  L pph #  `` `   0p8p `2   0pphf2   6jJpp^   6GP |2   Tv2 @>`` 8^  6G |2  Tv2 @>`` 8^  6G0v  Nv2 @ v2  Nv2 @h  ^  6Gp pp ^  6G pp L pph #   `  0p8p `2  0pphf2  6jJpp^  6GppP |2  Tv2 @> 8^  6Gpp |2  Tv2 @> 8^  6G0pp   BV@  NRef1.    ! BZ  ^Ref2>     "  B CDEFԔ  @`0z 0 P  #  0 p,$D  0|2 $ LA Wave0 P |2 % LA Wave P | & LA Wave` P z  `  * 0 ` ,$D 0fr + 6Ԕ ` &T 0` ,# -@  Z2 - s *0@`B . 0Do``` / <(a   4mV 2 0 6Ԕp  ,$D  0 3 <He@,$D  0 >Ecell = ERef(1) + Elj  ERef(2)     , H  0޽h ? ̙33_.  .. 4D w-(  r  S Pr`   l p   p ,$D 0  XAZig zag ` @ p  p ~2  Nv2 @ ~  Nv2 @ P ~  NMMMv2 @p   Htup  5Ref 1  ! Tv2 @Ԕp ,$D  0l &   & ,$D 0   XAZig zag  @ &   &  ~2   Nv2 @V F ~   Nv2 @V F P ~   NMMMv2 @& v   Nz&   5Ref 2  ' N?" ,$D  0" $ # tG0*fA?60%"p ,$D  0l    +  ,$D  0 * Nf?"  ~ )  (0e0e    B C DEF A@  > 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||   @S"  Fl 0 7 10 7,$D   0  BCPDEFoP @ P  `   P,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  <   4mV   B CPDE FoP @0 PPl , T ?"u7 Ecell EISM  l   0 ,$D  0 . T ?"@  LIon-selective membrane B / ZDo?" p " # lMMMv2 @?"pp ,$D  0 l   > ,$Dd  02 2 S ~̑vd @?"  ` ;+ 2 4 S ~vd @?" ` ;+ 2 5 S ~ܘvd @?"` P  ;+ 2 6 S ~vd @?" p @  ;+ 2 7 S ~vd @?"P P  ;+ 2 8 S ~vd @?" 0p  ;+ 2 9 S ~pvd @?"   ;+ 2 : S ~vd @?"`   ;+ 2 ; S ~vd @?"00 ;+ 2 < S ~ġvd @?" 0 ;+ 2 = S ~vd @?"  @  ;+ l  p C p,$D   0 A  <0e0e    BCDEF A@  Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||"@  S"   B # B0e0e    BQCDEF @  Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||Q5r#'@  S" p D <е`,$D  0 >Ecell = ERef(1) + Elj  ERef(2)     , H  0޽h ? ̙33  z0(  r  S `   r  S `P   ~  H?" P`  c $A ?? p H  0޽h ? ̙33  @$(  r  S `   r  S X  H  0޽h ? ̙33  P$(  r  S `   r  S <  H  0޽h ? ̙33  @8`(  n   0e0e    BC@DE F A@ f > 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||@@S"0 r  S `   2  c vd @>?"` 0 `    fv2 @?"` 0    fMMMv2 @?"0 ` t8   p   pB  TDԔ?"  @   TMMMjJ?" p    V0e0e    BCDE4F A@ f ) 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||  uL:#b dl @    S" z  `    0@,$D 0fr   6Ԕ ` &T 0`  # -@  Z2  s *0@`B  0Do```  <   4mV   Z Ԕ?"{  RExternal reference electrode   T ?" s ONon-conducting glass body   T( ?"P MV  RInternal reference electrode   Td ?"   lH+-responsive glass membrane4  B  ZDԔ?"@0 B @ ZDԔ?"  B  ZDԔ?" 0 B  TDԔ?" ` 0   T ?"06 OShielded connecting cable B  ZDԔ?"P H  0޽h ? ̙33!  =!5!p(-  (  r  S 0p   F 0 H     |    &0e0e    BC@DE F @ f > 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||@@S"0 2   c vd @>?"0 ` `    fv2 @?"` 0    fMMMv2 @?"0 ` N   p    pB  TDԔ?"  @   TMMMjJ?" p   \0e0e    BCDE4F @ f ) 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||  uL:#b dl @    S"   `   0@,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  < OT ] 4mV    Z  Ԕ?"H=  RExternal reference electrode B  TDԔ?"` 0   # lDv2 @?"0 P0 <  B  ZDMMM>?"P0B  ZDMMM>?"0 P@0 B  ZDMMM>?"0 @00 B  H?"p ,$D  0 ! Tv @?" ,$D  0l @P  %P @ ,$D  0  Z ?" P p \CO2(g):   " N?"@P  # N?" P  & T ?"0 @P  ? Flow Cell   f ' T, ?" HElectrode assembly fB ( ZDԔ?"p ) T! ?"0   ^(Gas-permeable membrane (silicone rubber)) )f|8 0  -0    T%?"0 ,$D  0 <  " , T$$ ?"   NaHCO3/H2Ob     T|. ?" d ,$D  0 .CO2 + H2O HCO3- + H+    N MMM>?"0 B   `D>?"0 @@0 B * ZDԔ?" @ H  0޽h ? ̙33   K C '((  x  c $:0p   F 0 H    |   &0e0e    BC@DE F @ f > 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||@@S"0 2  c vd @>?"0 ` `    fv2 @?"` 0    fMMMv2 @?"0 ` N   p    pB   TDԔ?"  @    TMMMjJ?" p    \0e0e    BCDE4F @ f ) 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||  uL:#b dl @    S"   `    0@,$D 0fr   6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  <? OT ] 4mV    ZDC Ԕ?"H=  RExternal reference electrode B  TDԔ?"` 0    f Hv2 @?"0 P0 <  B  TDMMM>?"P0B  TDMMM>?"0 P@0 B  TDMMM>?"0 @00 B  H?"p ,$D  0z @P   P @ ,$D  0  TK ?" P p \NH3(g):    H?"@P   H?" P   TP ?"0 @P  ? Flow Cell   f  T`T ?" HElectrode assembly fB   ZDԔ?"p ! TDY ?"0   SGas-permeable membrane (PTFE) fF 0  " 0   # T]?"0 ,$D  0 <  ! $ TH\ ?"   NH4Cl/H2Ob   % Txf ?" s ,$D  0 ,H2O + NH3 NH4+ + OH-  & N MMM>?"0 B ' ZD>?"0 @@0 B ( ZDԔ?" @ H  0޽h ? ̙33  *(  x  c $Xs`   r  S t  H  0޽h ? ̙33  QI(  r  S \x`    l @:0 @,$D  0   fv2 @?"mZ }   3 r v2 @?"m} Z  GNa+(    fv2 @?"m}   TЂ ?"@* 0 A Whole blood   f  ZHI* jJ?" @ Z    ZHI* jJ?" Z @ B   ZDjJ?" @    TЇ ?"@  N$  A Cells (45%)      T܋ ?"@ D:  C Aqueous phase    Tl ?"( :PZ FLipids, proteins   ZHI* jJ?"PP   T ?"  <Plasma vl @p @p,$D 0   `v @?"pp  `   @,$D 0fr  6Ԕ ` &T 0` # -@  Z2  s *0@`B  0Do```  <t   4mV v   0e0e    BC DE F A@ f Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||  @S"`  T ?" 5X,$D  0 Since potentiometry measures the activity of the ion at the electrode surface, the measurement is independent of the volume of sample.Z !L tH  0޽h ? ̙33  &(  x  c $`   8 0z@:  @ `p  C xXv2 @?"0@:  GNa+(   # lv2 @?"0z@   fv2 @?"0`p,$D  0  T Ԕ?"p`pz @p A p ,$D  0   `v @?"pp  `   @,$D 0fr   6Ԕ ` &T 0` !# -@  Z2 " s *0@`B # 0Do``` $ <   4mV | %  &0e0e    BC DE F @ f Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||  @S"`c & H ?" `P.,$D  0 In indirect potentiometry, the concentration of ion is diluted to an activity near unity. Since the concentration will take into account the original volume and dilution factor, any excluded volume (lipids, proteins) introduces an error, which usually is insignificant.Z ! H  0޽h ? ̙33  P(  r  S  `     S  <$  0  H  0޽h ? ̙33  $(  r  S `   r  S P  H  0޽h ? ̙33   d \   (  r  S `   hz 0z@:   @ 0 ,$D  02  3 rv2 @?"0@:  z Na+ 140 mM2     fv2 @?"0z@fl  @  @ ,$D  08   C xv2 @?" 0  z Na+ 140 mM2     # lv2 @?" @ 0 l 0 0 0 ,$D  0   # lv2 @?"0,$D  08   C xHv2 @?"0   z Na+ 138 mM2    T Ԕ?"p 0 l  0 0 ,$D  0   fv2 @?" 0,$D  02  3 rv2 @?" 0   z Na+ 130 mM2     T Ԕ?"p H  0޽h ? ̙33  P(  r  S `     S t <$  0  H  0޽h ? ̙33  $(  r  S `   r  S    H  0޽h ? ̙33  $(  r  S `   r  S l   H  0޽h ? ̙33  qi   (  ~   H?"0P`Pr  S 0 `   >l       ,$D  02  S ~vd @?"    Z` ?" /  ^K+@ `f`f`ff  s *A ??    N ?" , yValinomycin is an antibiotic that has a rigid 3-D structure containing pores with dimensions very close to the un-hydrated radius of the potassium ion. Valinomycin serves as a neutral carrier for K+.j 2  $  $H  0޽h ? ̙33  h`0 (  r  S P`     N?" <     Z?"P V2  S ~ vd @?"e e ,$D  0 fCa++F fffl p8  p8,$D  0$  TX% ?"pb  di-p-octylphenyl phosphate( $  h  c $A ??&8    TL+ ?"S  > PVC membrane   B   ZDԔ?" @H  0޽h ? ̙33  @ (  x  c $`     N1?" <  V2  S ~(5vd @?"` p@` ,$D 0 fCa++F fff  Z?"0l  ,$D 0  T0: ?"g0 ANeutral carrier h  c $A ??    T= ?" 0 @Inert membrane H  0޽h ? ̙33  P$(  r  S C`   r  S D 0  H  0޽h ? ̙33  ` '(  r  S H`     NL?"p <    N\L ?"O?_  Current (mA) 6     TdT ?"@ .Applied potential (V) 6    F0e0e    BCfDE(F A@  Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E|| c`cf@c`{aQYA @   S" P- C,$D  0   v0e0e    BC0DELF$ A@  Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E||0\ ,LX_|WK cYPa!@      S"* ,$D  0   V0e0e    B8CDE4F A@  Ԕ 8c8c     ?1 d0u0@Ty2 NP'p<'pA)BCD|E|| 'YEE1(!{ rNo8 @    S"  ,$D  0B   ZDfo?" ,$D  0    TZ ?"  ,$D 0 GHalf-wave potential B @ ZDfo?" 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