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ELECTROQUÍMICA
1FQ UNAM
alejandro baeza
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BIOELECTROQUÍMICA
2FQ UNAM
alejandro baeza
![Page 3: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/3.jpg)
BIO
ELECTROQUÍMICA
ANALÍTICA
3FQ UNAM
alejandro baeza
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Bioelectroquímica:
Caracterización termodinámica, cinética procesos redox:Fosforilación oxidativa mitocondrial
fotosíntesismetaloenzimas, DNA-metal
cinética enzimáticabiofarmacia
4FQ UNAM
alejandro baeza
![Page 5: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/5.jpg)
Bioelectroquímica:
Transporte en membranas:
bicapas, liposomas, interfases neuronales
electrofiosiología
canales iónicos5
FQ UNAM alejandro baeza
![Page 6: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/6.jpg)
BioelectroquímicaAnalítica
BIO ELECTRO ANÁLSIS
BIOSENSORES
ENZIMATICOS, INMUNOLÓGICOS,MICROBIOLÓGICOS
Especiación de metabolitos
bioquímica clínica
control y desarrollo farmacéutico
química forense
6FQ UNAM
alejandro baeza
![Page 7: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/7.jpg)
CARACTERIZACIÓN ELECTROQUÍMICA
7FQ UNAM
alejandro baeza
![Page 8: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/8.jpg)
Estrés oxidativo
8FQ UNAM
alejandro baeza
![Page 9: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/9.jpg)
H.Prado, P. Diaz. J.L. Ortiz and Alejandro BaezaPolarographic Determination of Km´and v maxOf Glutathione ReductaseCurrent Separations 20-4(2004)117-122
Vidrio H., Medina M, Gonzalez R, Diaz P, Lorenzana M., A. BaezaSemicarbazide-Sensitive Amine Oxidase Substrates potentiateHydralazine Hypotension: possible role of Hydrogen PeroxideThe Journal of Pharmacology and Experimental Therapeutics 307-1(2003)497-504
WE: DME
ER AE N2
P. Diaz, M. Lorenzana., H. Vidrio and A. BaezaHydrogen Peroxide electroanalytical determination in bilogical liquid samplesProc. West. Pharmacol. Soc. 45 (112-113
EJEMPLO 24.
EJEMPLO 25.
EJEMPLO 26.
9FQ UNAM
alejandro baeza
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10FQ UNAM
alejandro baeza
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DC and DPPMicropolarographic
cell
(vol. = 0.5 mL)
ER
AE
WE: DME
11FQ UNAM
alejandro baeza
![Page 12: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/12.jpg)
12FQ UNAM
alejandro baeza
![Page 13: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/13.jpg)
13FQ UNAM
alejandro baeza
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Correlación
Estructura - actividad
14FQ UNAM
alejandro baeza
![Page 15: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/15.jpg)
Estudiosen mediosno acuosos
como laMembrana
Celular
15FQ UNAM
alejandro baeza
![Page 16: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/16.jpg)
HorminonaNeuro activo
16FQ UNAM
alejandro baeza
![Page 17: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/17.jpg)
17FQ UNAM
alejandro baeza
![Page 18: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/18.jpg)
¡Radical Neutro!
18FQ UNAM
alejandro baeza
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example : oxidation of dihydropyrimidones, DHPM
N
NH
O
O
O
H
R
R Position R Position R Position
H - OH 2 OH 2, 4
F 3 OH 3 NO2 4
CH3 3 OH 4Derivative of 2-metoxi
cinamaldehyde
OCH3 4 OCH3 3, 4, 5 Derivative of naphtaldehyde
EJEMPLO 2: Estudio potencial-pH en medio orgánico tamponado:
antiepilépticos
19FQ UNAM
alejandro baeza
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m = 110.57 [mV/pH]
m = 31.50 5 [mV/pH]
1350
1450
1550
1650
1750
7 9 11 13 15 17
Epa, [m
V]
pHcalculado
m = 0.0 [mV/pH]
Plot Epa = f (pH) of a DHPM in acetonitrile
buffer solutions
J. M. Aceves, R.Miranda, A.Baeza, E. Galicia, R. Osnaya and C. O. Kappe.
Electrochimica Acta, Submited(2006)
E
pH
20FQ UNAM
alejandro baeza
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Electrooxidación de una familia de fenoles como sustratos de oxidasas de interés biotecnológico
Arturo García, A. Baeza. Facultad de Química (estancias cortas de investigación)
Marcela Ayala, Rafael Vazquéz-DuhaltInstituto de Biotecnología.UNAM.
agosto 2006
Hidroquinona
4-bromofenol
4-metoxifenol
4-etoxifenol
4-clorofenol
Fenol p-cresol
4-acetamidofenol4-hidroxibenzonitrilo
4-etilfenol4-nitrofenol
ácido 4-hidroxibenzoico
4-hidroxiacetofenona
0.500
0.600
0.700
0.800
0.900
1.000
1.100
1.200
1.300
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14E
ap/E
.N.H
.
Número de compuesto
Potencial de pico anódico con respecto al E.N.H.
EJEMPLO 31.
21FQ UNAM
alejandro baeza
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:Mayen R., Baeza A., Ibañez JSimulttaneous determination of nickel and cadmium by Differential Pulse PolarograpyAnalytical Sciences 18 (2002)1-3
Jimenez N., Roman A.,Baeza A., Sanchez A., Valderrama B.Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas mediterraneaJournal of Molecular Catalysis: B Enzymatic 19-20(2002)437-441
J. Verdín, R. Pogni, A. Baeza, M Camila, R Rossi, R.Vázque-DuhaltMechanism of versatile peroxidase inactivation by Ca(II) depletionBiophysical Chemistry 121 (2006)163-170
Microelectrochemical cells
E. Torres, A.Baeza A., R vázquez-Duhalt.Chemical Modification of heme group improves affinityOf hydrophobic substrates in organic media.Journal of Biotechnology 117 (2005)73-82
22FQ UNAM
alejandro baeza
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F
ENCB
23FQ UNAM
alejandro baeza
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BIOELECTROANALISIS24
FQ UNAM alejandro baeza
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Sensores y biosensores
25FQ UNAM
alejandro baeza
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GSH -2e Hg-SG
26FQ UNAM
alejandro baeza
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27FQ UNAM
alejandro baeza
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I/ se forma la capa de Hg°
Hg (II)
+2e
II/ se forma la capa Hg-SH
-2e -2H+
III/ se prueba sensor
28FQ UNAM
alejandro baeza
![Page 29: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/29.jpg)
29FQ UNAM
alejandro baeza
![Page 30: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/30.jpg)
30FQ UNAM
alejandro baeza
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31FQ UNAM
alejandro baeza
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32FQ UNAM
alejandro baeza
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microbiosensores
EJEMPLO 12: microsensor de ác. ascórbico a base de extracto de pepino.
-60
-58
-56
-54
-52
-10 -5 0
DE
(mV
)Curva de Calibración
DE = f(logC) a t = 370s
Ascorbato oxidasapepino
33FQ UNAM
alejandro baeza
![Page 34: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/34.jpg)
Glucosa oxidasa
34FQ UNAM
alejandro baeza
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35FQ UNAM
alejandro baeza
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La Jornada15 de enero de 2004
Muhammed Akthar, V. Espinoza, A. Baeza A. M QaziPakistan Journal of Soil Sciences 22(2003)41-46
V. Espinosa, Muhammed Akhtar, A.Baeza, AbdulMujeebPakistan Journal of Biological Sciences 8[1](2005)61-62
pH?
EJEMPLO 5: Determinación del pH en tierra en cultivo de trigo en simbiosis vegetal con Lupinus directamente enrizoma en tierra:
36FQ UNAM
alejandro baeza
![Page 37: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/37.jpg)
Microelectrochemical cells
V = 50 LPANI
Polímeros conductores en la construcción de:
37FQ UNAM
alejandro baeza
![Page 38: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/38.jpg)
MICROELECTRO-ANÁLISIS DE BAJO COSTO CRONOAMPEROMÉTRICO Y VOLTAMPEROMÉTRICO DEL SISTEMA
ACOPLADO FERRICIANURO-GLUCOSA MEDIADO POR GLUCOSA OXIDASA.
Guillermo H. Álvarez Arizabalo, Alejandro Baeza
Voltamperometrí a Barrido de potencial
Cronoamperometríade pulso directo
Voltamperometrí a Barrido de corriente
Estancias tuteladas QFB 38FQ UNAM
alejandro baeza
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Allan Noé , estancias tuteladas QFB
39FQ UNAM
alejandro baeza
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N
N
N
O-Na+
Cl
OO
Cl
CONTROLY
DESARROLLOANALÍTICO
FARMACÉUTICO
40FQ UNAM
alejandro baeza
![Page 41: BIO E LECTROQUIMICA ANALÍTICA - UNAMdepa.fquim.unam.mx/amyd/archivero/BIOELECTROQUIMICA_2009_7999.pdf · Alkali halide-resistant catalisis by the multipotent oxidase from Marinomonas](https://reader034.vdocuments.us/reader034/viewer/2022042016/5e74a8f66929af3902224af7/html5/thumbnails/41.jpg)
0
0.2
0.4
0.6
0.8
1
1.2
0 0.2 0.4 0.6 0.8 1
Y
Volumen agregado (mL)
Valoración conductimétrica de H+ con OH-
EJEMPLO 13:
0
10
20
30
40
50
60
0 0.2 0.4 0.6 0.8 1 1.2
E(m
v)
mL NaOH 0.1M
titulacion naproxeno/Vantin
(1)
(2)
(3)
(4)
EJEMPLO 14
EJEMPLO 15:
EJEMPLO 16:pureza de agua:
41FQ UNAM
alejandro baeza
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Low cost sampled current pulse voltammetry:
Karl Fisher H2O titration
MIM-I
A. Baeza, Workshop in the 3rd International Microscale Chemistry SymposiumMexico City. 2005
3 electrodes microcell
Water content determinationChronoamperometric end-point
Adrián de Santiago, 2002
EJEMPLO 22.
42FQ UNAM
alejandro baeza
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-20
0
20
40
60
80
100
120
0 500 1000 1500 2000 2500
I (m
A)
E (mV)
Gráfica I=f(E)
EBS
EBS/Ác. ascórbico
Do = 1.79x10-5 cm2/s
Example 23: Ascorbicacid oxidation
Voilà!
EJEMPLO 23. Obtención de parámetros fisicoquímicos válidos: Coef. de difusión.
43FQ UNAM
alejandro baeza
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acetaminofen
44FQ UNAM
alejandro baeza
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FACULTAD DE QUIMICA
PROGRAMA DE ESTANCIAS TUTELADAS 2009-I
Estudio microelectroanálitico de Diyodohidroxiquinoleina en tabletas
DIODOQUIN® 650mg
Estancias Tuteladas QFBARCADIO CRUZ VELASCO
I2
46FQ UNAM
alejandro baeza
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-4E-05
-3E-05
-2E-05
-1E-05
-1E-19
1E-05
2E-05
0 10 20 30 40 50 60 70
I(A
)
Tiempo (s)
Cronoamperometria de Yodo
BLANCO
50mL Yodo 0.088N
100mL Yodo 0.088N
150mL Yodo 0.088N
200mL Yodo 0.088N
250mL Yodo 0.088N
300mL Yodo 0.088N
350mL Yodo 0.088N
400mL Yodo 0.088N
450mL Yodo 0.088N
500mL Yodo 0.088N
47FQ UNAM
alejandro baeza
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Curva de calibraciónI g corriente a
0 -0.785
563.4 -3.039
1126.8 -4.836
1690.2 -6.59
2253.6 -8.351
2817 -9.1
3380.4 -11.05
3943.8 -12.9
4507.2 -14.5
5070.6 -16.15
5634 -17.53
y = -0.0029x - 1.3265R2 = 0.9969
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
0 1000 2000 3000 4000 5000 6000
A
I g
Estándar I
48FQ UNAM
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• Muestra eq. 5mg P.A.
• 50mL KI 0.1M
• Alícuota 3mL
Valoración Diodoquin
-1.75E-06
-1.40E-05
-1.20E-05
-1.00E-05
-8.00E-06
-6.00E-06
-4.00E-06
-2.00E-06
0.00E+00
0 10 20 30 40 50 60 70
I(A
)
Tiempo (s)
Cronoamperometría de DiodoquinEcuación de regresión:
I=-0.0029gYodo -1.3265
gYodo=(-1.75+1.3265)/-0.0029
gYodo=(146.03/3mL)
gYodo=2433.9 = 2.4339mg
49FQ UNAM
alejandro baeza
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Prueba
Muestra 1 Muestra 2
FEUM (%)Cronoampero
metría (%)FEUM (%)
Cronoampero
metría (%)
1 111.1 118.4 110.6 107.6
2 113.7 118.6 113.6 97.0
3 121.6 120.9 110.6 101.8
4 121.6 111.5 113.6 118.2
5 129.6 109.0 119.6 113.7
6 111.4 111.7 116.6 116.5
7 111.4 123.9 113.6 101.2
8 118.9 110.6 113.6 116.2
9 130.0 111.6 110.6 121.9
10 118.9 117.4 119.6 122.0
11 118.0 115.8 109.4 119.9
12 126.3 113.4 103.2 121.7
13 126.3 111.6 109.4 97.6
14 122.6 109.4 97.4
15 118.9 109.4 95.0
Promedio 120.0 115.0 112.2 109.8
s 6.3 4.6 4.3 10.5
Error relativo 4.2 2.1
-300
-200
-100
0
100
200
300
-15
00
-10
00
-50
0 0
50
0
10
00
15
00
20
00
25
00
I [mA]
E [mV]
Teresita Rode, Serv. Soc. QFB
Electroanálisis de penicilinas
2I-
I2
50FQ UNAM
alejandro baeza
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MicrotitulaciónBifásica deBromohidrato
De dextrometorfán
51FQ UNAM
alejandro baeza
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Microelectrodos en tejidoSEROTONINA
53FQ UNAM
alejandro baeza
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54FQ UNAM
alejandro baeza
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55FQ UNAM
alejandro baeza
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Electrodo de cobre (referencia)
Monitoreo del pH in situ en cultivos microbianos
Termometro clinico
Electrodo de Wolframio (sensor)
Matraz con “medio minimopara E. coli“
Asa
-194
-192
-190
-188
-186
-184
-182
-180
27-6-200428-6-200429-6-200430-6-2004 1-7-2004 2-7-2004 3-7-2004 4-7-2004 5-7-2004 6-7-2004
Po
ten
cia
l (v
olt
ios)
días (fecha)
Medición del potencial para obserevar el desarrollo de microorganismos
EJEMPLO 6:
56FQ UNAM
alejandro baeza
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57FQ UNAM
alejandro baeza
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58FQ UNAM
alejandro baeza
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gracias59
FQ UNAM alejandro baeza