! "
!"#$% & '
(&&)* + (,&-& +
. / + 0
1 23)%
#"$"$
45 6%" (&&)* / *%7 8%7% 4
1
(&&)*% 5 9
/ : ;%7 <"$% & / *%7(&&)*
./*#=
(&&)**
0 # % > ?
λ : *66 *"" *"*
.2 ) 0 λ : ;;7 ;!6 @** .2 A0% > / 8%7
(&&)* ./#(&&)**0 * % )
? *"6 .2 ) 0 ;"; ;;#
;8< @6# .2 A0%
400 450 500 550 600 650 700 0.0
0.2 0.4 0.6 0.8 1.0 1.2
500 550 600 650 700
0.00 0.02 0.04 0.06 0.08 0.10
absorbância
comprimento de onda (nm)
absorbância
comprimento de onda (nm)
pH 4.0 pH 7.0
5 6%"0 > (&&)*$: ";B, / *%7 8%7% C : 7%# %
% & ' & (εεεε)
D
(&&)* / 8%7 *%7 % 4
? E
1 E %
2 F
ε
ε . 3"0
. 0 ?
A%
D 1 E 1 '
. G
5 6%#0% H '
G α ε
0.0 5.0x10-6 1.0x10-5 1.5x10-5 2.0x10-5 2.5x10-5 0.0
0.2 0.4 0.6 0.8
α αα α abs644 nm
[TPPS4] (M)
5 6%#0 H ε @** (&&)* / *%7%
I ε (&&)* / 8%7 Fε;"; : ."%6 ± 7%7"0 × "7*,"
"J ε;;# : .;%!± 7%7<0 × "76," " ε;8< : .;%;± 7%7!0 × "76," " ε@6# :
.6%"@±7%780 ×"76," " / *%7 ε;!6 : .!%7±7%#0× "76," " ε@**
: .6%#@±7%7*0×"7*," "%
> 1
' E ? %
K E E 1
(&&)*
!
"#
! $ %
> / *%7 D C ?
% K . L "7 0
% D
E D C 7%7< 7%@ ,
D C% & (&&)*$: "7µ, λ : @** ?
' 1 D C . 0 . 0
: "%# ±7%7# E D C %
4 M
+ ' *"6
.5 6%6 6%*0% > D C%
380 400 420 440 460 480
0.0 0.2 0.4 0.6 0.8 1.0
1.2 [NaCl] = 0 [NaCl] = 0.3 M t = 0 [NaCl] = 0.3 M t = 5 min
absorbância
comprimento de onda (nm)
5 6%60 , (&&)*$: "7µ, / *%7
D C$: 7%6 , % C 7%# %
0 5 10 15 20 25 30 35
0.0 0.2 0.4 0.6 0.8 1.0
t2 t1
absorbância normalizada
tempo (min)
413 433 491 644 707
5 6%*0 , (&&)*$: "7µ, /
*%7 D C$: 7%6 , %
4 . "0 +
*"6 % K
% D
*!" 878 .5 6%;0% >
? #
5 6%*%
400 500 600 700
0,0 0,2 0,4 0,6 0,8 1,0 1,2
661
600 650 700 750
0.00 0.15 0.30 0.45 0.60 0.75 0.90 1.05
absorbância
comprimento de onda (nm)
a b
644 433
707 491
ab so rb ân ci a
comprimento de onda (nm)
5 6%;0 . 0 > (&&)* $: ";µ, / *%7 1 .−0
D C$: 7%6 , @7 . 0J 7%# % . 0 >
(&&)*$: #;µ, D C$: 7%" , %
4 " #
E N D C ( 6%"%
! C (&&)*
D C %
& '()* & "#'+ ,µµµµ) & "#'+ -,µµµµ)
./. ( * -( * ./. ( * -( *
/0 /0, ,±±±±/ -±±±±/ 111 111 111 /, /2/ 0±±±±/ /±±±±/ 111 111 111 /# /2# - .±±±±/ - ±±±±/ ,- /,±±±±/ /..±±±±/ / /2# ±±±±/ 3±±±±/ ,/ /±±±±/ /0±±±±/ /- /., # /±±±±/ ,/±±±±/ #, /.±±±±/ ±±±±/ / , /0- /±±±±/ / ±±±±/ # ±±±±/ ,±±±±/ //2 111 4 0/ 111 /3- ±±±±/ - 2±±±±/
4 D C
(&&)* % 4 M
D= + ./*#=(&&)**0% C
9 1 D C
. 0 1 %
% & * !
+ ,
( E E (&&)* / ? 1
D C
% 4 / #%7 "7 1 D C 6%7
8%7 % 4 D C ? 7%6 ,%
5 E
/ ;";
(&&)* 878 % I M (&&)*
D C% C ' /
% O ?
%
) F
] .
[
] .
log [
da desprotona Forma
protonada Forma
pk
pH = a+ .6%#0
D F
4 (&&)* 1 D C
5 6%@ 5 6%8
(&&)* D C%
500 550 600 650 700 0.0
0.1 0.2 0.3 0.4 0.5
absorbância
comprimento de onda (nm)
pH 4.0 pH 5.0 pH 7.0
5 6%@0 , (&&)* / 1 D C%
500 550 600 650 700 750
0.0 0.2 0.4 0.6 0.8 1.0
absorbância
comprimento de onda (nm)
[NaCl] = 0.3 M pH 4.0 pH 4.5 pH 7.0
5 6%80 , (&&)* / D C%
I 9 1 D C
;%7 ? *%; 5
6%<%
3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 0,0
0,2 0,4 0,6 0,8 1,0
pKa= 4.5
pKa= 5.0 [NaCl] = 0 [NaCl] = 0.3 M
A/ApH 4.0
pH
5 6%<0 4 ' .40 (&&)*$: "7µ, / 1 .− −0
.− −0 D C% D 1 D C 4 λ: ;"; λ:
878 %
I + 9 !$% >
D C D=
/*#=
(&&)**
% 4
D= /= / (&&)*% &
. /0% K
9 .∆ 90 F
∆ Ψ .6%*0
Ψ G M
(&&)* ? D= "7*$%
I '
!$ 9 (&&)*
%
5 $ 6 6 "#
4 + # 6
+ M % 4 # ?
*"6 % 4 ?
% 4P "7$
M (&&)* ?
*"6 % >
' E D C
D C ? Q "777 ?
(&&)*% D
" M %
4 D C$: 7%6 ,
9 *%; / *%7 (&&)* % 5
*"6
% O
%
D *"6 M
G *"6 % R
+ / . G
"%;%60% > 23) 1
%
4 6 ?
+ / *!"
878 % D *!" M
S (&&)* !$ +
*66
4 878 M
"7$% >
1 .5 6%*0% K 878
M S% &
+ @**
% T
/*#=(&&)** D C M S
%