a base da espectrometria de massas - uel portal · mass spectra and isotopes the nobel prize in...
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A base da espectrometria de massas
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JJ Thomson's 'Plum Pudding Model' of the atom, a sphereof positive charge containing electrons
The father of MS and the first massspectrometrist to win the Nobel Prize.
Pure species and mixtures
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Mass spectra and isotopes
The Nobel Prize in Chemistry 1922"for his discovery, by means of his mass spectrograph, of isotopes, in a largenumber of non-radioactive elements, and for his enunciation of the whole-number rule"
Francis William AstonAt the end of 1909 he accepted the invitation of Sir J.J.Thomson to work as his assistant at the Cavendish Laboratory, Cambridge, onstudies of positive rays. It was during this period that he obtaineddefinite evidence for the existence of two isotopes of the inert gasneon.
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EI : Ionização por elétrons(Dempster e Nier)
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• Moléculas neutras, na fase gasosa (dessorçãotérmica), a uma pressão típica de 10-5 torr, são bombardeadas por elétrons, com energia típica de 70 eV. Ocorre principalmente a retirada ou captura de um eléctron formando íons M+. ou M-.. Íons positivos são em geral predominantes (~100 vezes mais). M-. se tornam importantes para moléculas com alta EA.
M + e- (70 eV) → M+. (~ 5 eV) + 2e- (65 eV)
Princípio Geral de EI
M M
e-
+
F2
F4F3
F1
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Princípios Gerais
• Processo unimolecular. Os íons formados são rapidamente extraídos da fonte de ionização pelo eletrodo de repulsão("repeller“).
• Íons moleculares são formados com excesso de energia interna e se fragmentam total ou parcialmente.
• EI é bastante popular: produz tanto o íon molecular (massa) como também fragmentos (estrutura); espectros reprodutíveis; bibliotecas de espectros de EI a 70 eV; estável; fácil de operar; alta sensibilidade.
• Aplica-se a moléculas de média e baixa polaridade e baixo peso molecular (~500u), voláteis e termo-estáveis: moléculas orgânicas relativamente pequenas.
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Princípios Gerais
• Quando o íon molecular não é observado (devido a dissociação excessiva), é inútil diminuir a energia dos elétrons.
• Uma em cada 103-105 moléculas que entram na fonte de EI éionizada.
• EI ocorre em ~10-16 s. Ocorre sem mudanças nas distâncias internucleares (Frank-Condon).
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• Esquema Geral
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• A diminuição da energia dos elétrons provoca uma queda brusca nas intensidades absolutas de todos os íons, mas um aumento na intensidade relativa do íon molecular.
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Espectros Típicos de EI a 70 eV
2-Hydroxy-1,2-diphenyl-ethanone
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(mainlib) 1-Octanol10 20 30 40 50 60 70 80 90 100 110 120 130 140
0
50
100
15 18
27
29
37
39
41
45 50
56
62
70
73 77
84
91 97 101 112
OH
(mainlib) 1-Octene10 20 30 40 50 60 70 80 90 100 110 120
0
50
100
14
27
29
31
39
41
43
45
55
59 62
70
72 77
83
91 97
112
(mainlib) 2-Octene10 20 30 40 50 60 70 80 90 100 110 120
0
50
100
15
2729
32
39
41
51
55
67
70
77
83
97
112
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Alguns espectros de EI apresentam dissociação excessiva, outros pouca dissociação.
M+. = massa e isótopos
F+ = estrutura
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Espectro de Massas: Ionização por Elétrons (EI)
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Isômeros C3H6O
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M-1 Perda de hidrogênio radicalar M - .H
M-15 Perda de metil radicalar M - .CH3
M-29 Perda de etil radicalar M - .C2H5
M-31 Perda de metoxi radicalar M - .OCH3
M-43 Perda de propil radicalar M - .C3H7
M-45 Perda de etoxi radicalar M - .OC2H5
M-57 Perda de butil radicalar M - .C4H9
M-2 Perda de hidrogênio M – H2
M-18 Perda de água M – H2O
M-28 Perda de CO ou etileno M-CO ou M-C2H4
M-30 Perda de formaldeido M- CH2O
M-32 Perda de metanol M-CH3OH
M-44 Perda de CO2 M-CO2
M-60 Perda de ácido acético M-CH3CO2H
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(mainlib) 1-Octanol10 20 30 40 50 60 70 80 90 100 110 120 130 140
0
50
100
15 18
27
29
37
39
41
45 50
56
62
70
73 77
84
91 97 101 112
OH
(mainlib) 1-Octene10 20 30 40 50 60 70 80 90 100 110 120
0
50
100
14
27
29
31
39
41
43
45
55
59 62
70
72 77
83
91 97
112
Íon Molecular
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“Chemical Ionization”CI
Munson and Field - 1966
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Princípios Gerais
• Ionização por reação química (ex: protonação : MH+). A exotermicidade da reação controla a extensão dos processos dissociativos.
• Gases ionizantes típicos: metano, isobutano, amônia.
• Como em EI, aplica-se a moléculas de média e baixa polaridade e baixo peso molecular (~500u), voláteis e termo-estáveis: "moléculas orgânicas". Uma aplicação típica de CI ocorre para substâncias que não apresentam o íon molecular por EI.
• Adutos formados entre M e o íon reagente podem ser observados (Ex. M-NH4
+). Estes adutos podem diferenciar isômeros.
• CI é uma técnica branda de ionização, por provocar pouca ou nenhuma fragmentação da molécula ionizada.
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CI – IONIZAÇÃO QUÍMICA
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Ionização Química (CI).
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ReaçãoÍon/molécula
50 eV+ e- e-+
térmicaCH4 + e-
70 eV+CH4 + H+CH4
CH3+
H2++CH4 CH4+ CH5
+ + CH3
CH3+ + CH4
CH4++ CH4
C2H5+
C2H3+
C3H5+
+
+
+
H2
H2
H2
H+
+CH4
CH2+
CH2+
C2H3+
Controle da Exotermicidade da Reação: Extensão de Fragmentação
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Ionização Química (CI).
• Ionização Química Positiva:Metano:
CH4 + e -----> CH4+. + 2e ------> CH3
+ + H.
CH4+. + CH4 -----> CH5
+ + CH3.
CH4+. + CH4 -----> C2H5
+ + H2 + H.
Isobutano:
i-C4H10 + e -----> i-C4H10+. + 2e
i-C4H10+. + i-C4H10 ------> i-C4H9
+ + C4H9 +H2
Amônia:
NH3 + e -----> NH3+. + 2e
NH3+. + NH3 ------> NH4
+ + NH2.
NH4+ + NH3 --------->N2H7
+
• Ionização Química Positiva:Metano:
CH4 + e -----> CH4+. + 2e ------> CH3
+ + H.
CH4+. + CH4 -----> CH5
+ + CH3.
CH4+. + CH4 -----> C2H5
+ + H2 + H.
Isobutano:
i-C4H10 + e -----> i-C4H10+. + 2e
i-C4H10+. + i-C4H10 ------> i-C4H9
+ + C4H9 +H2
Amônia:
NH3 + e -----> NH3+. + 2e
NH3+. + NH3 ------> NH4
+ + NH2.
NH4+ + NH3 --------->N2H7
+
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Reserpina CH4 CI
Reserpina EI 70 eV
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MS ?
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APCI – “Atmospheric Pressure Chemical Ionization”
APPI – “Atmospheric Pressure Photo-Ionization”
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SIMS – IONIZAÇÃO POR ÍONS SECUNDÁRIOS1970 Benninghoven
ion guns (LMIG) Ga+ and In+
Csþ ions give higher yield
SF5+, Bi+n, Au+n
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FAB – IONIZAÇÃO POR BOMBARDEAMENTO DE ÁTOMOS ACELERADOS (liquid SIMS)
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Xe + e- IONIZAÇÃOXe
+
ÍON LENTO
Xe+
ÍON LENTO
ACELERAÇÃOXe
+
ÍON RÁPIDO
Xe+
ÍON RÁPIDO
ÁTOMO LENTO
ÁTOMO LENTO
Xe+TROCA DE ENERGIA + Xe
ÁTOMO RÁPIDO
Xe+
ÍON LENTO
Formação de átomos acelerados
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Índice de popularidade - FAB
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Matrizes
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Efeito da Matriz
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Sistema CF-FAB (continuous-flow FAB)
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Yamashita, M.; Fenn, J.B., J. Phys. Chem. 88 (1984) 4451.
Whitehouse, C.M.; Dreyer, R.N.; Yamashita, M.; Fenn, J.B., Anal. Chem. 57 (1985) 675.
Fenn, J.B.; Mann, M.; Meng, C.K.; Wong, S.F.; Whitehouse, C.M., Science 246 (1989) 64.
"Electrospray Ionization for Mass Spectrometry of Large Biomolecules,“
The Nobel Prize in Chemistry 2002
"for the development of methods for identification and structure analyses of biological macromolecules"
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Popularidade do Electrospray
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Príncipio Geral
• Uma solução acidificada ou basificada da amostra (ou “neutra” de um sal) é submetida a um spray eletrolítico sob pressão atmosférica. Um fino “spray” (aerosol) se forma (cone de taylor) na presença de um alto campo elétrico (+4000V ou – 4000V). O contra-íon é oxidado oureduzido e formam-se gôtas com excesso de carga (positiva ou negativa). O solvente das gôtas evapora com redução de volume, e as gôtas se subdividem. Eventualmente, devido a alta repulsão entre os íons de mesma carga, ou se formam gôtas contendo apenas um íon (modelo CRM) ou íons são expelidos das gôtas para a fase gasosa (modelo IEM de evaporação de íons).
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COHO
NH2
HCl
NaOHC
O
OH2N
-
COH
OH3N
+C
OH
OH3N
+Cl-
CO
OH2N
-Na+
ESI Positivo
ESI Negativo
+ 4.000 V
- 4.000 V
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“Enganando” as moléculas neutras com curvas
Z-spray (Micromass)
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Fonte Z-spray
0.00 0.40 0.80 1.20 1.60Time
ESI+, Full Scan
Extracted at m/z 256
Total Run Time > 25 Hr
More than 500 mg salt
n = 1n = 509
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MS
Fonte de ESI: Ionização sob pressão atmosférica !
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Positive ESI-MS m/z spectrum of the protein hen egg white lysozyme
Proteínas
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Ionização a Pressão Atmosférica (API). Eletrospray (ESI)/Pequenas moléculas
Possibilidade de formação de íons com múltiplas cargasPossibilidade de formação de íons com múltiplas cargas
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Espectros de ESI-MS típicos : “Pequenas Moléculas”
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Espectros de ESI-MS típicos : “Pequenas Moléculas”
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n=(M1- 1)/(M2 –M1)n=(1131.2 – 1)/(1211.9-1131.2) = 14,1
M = n(M1 – 1) ⇒ 14 (1131.2 – 1)= 15822,8
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MALDI vs ESI
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Popularidade do Electrospray
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MS ?
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MALDI – “Matrix-Assisted Laser Desorption Ionization”
(Karas & Hillenkamp - 1987)
The Nobel Prize in Chemistry 2002
"for the development of methods for identification and structure analyses of biological macromolecules"
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Popularidade do MALDI
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MALDI “…fazendo um elefante voar !”
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MALDI “…fazendo um elefante voar !”
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MALDI- IONIZAÇÃO/DISSORÇÃO A LASER ASSISTIDA POR MATRIZ
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MALDI- IONIZAÇÃO/DISSORÇÃO A LASER ASSISTIDA POR MATRIZ
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Matrizes
• Razão matriz-amostra: 100:1 a 5000:1
(1) α-cyano-4-hydroxycinnamic acid : CCA
(2) 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid) : SA
(3) 2,5-dihydroxybenzoic acid.
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• Prepara-se solução da amostra e matriz (pequenas moléculas orgânicas). O solvente é evaporado resultando em uma solução sólido-sólido que é depositada sobre a superfície da sonda. Esta solução é então irradiada com laser. Ocorre aquecimento localizado e seletivo. A matriz absorve fortemente a radiação do laser. Ocorre a evaporação rápida da matriz e a molécula ionizada (ex: MH+) éentão liberada para a fase gasosa, e acelerada em direção ao analisador de massas pelo alto potencial (20.000 V) aplicado à sonda.
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Espectros e Aplicações
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MALDI de polímerosMALDI de polímeros
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Conceitos Importantes
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Notação dos Espectro de Massas
• Informações Estruturais• Informação da Massa do Compostos
m/z0 50 100 150 200 250
Ion
Abun
danc
e (%
)
0
20
40
60
80
100
Eixo y: Abundância %Eixo x: Relação massa/carga (m/z)
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Isóbaros
São moléculas com diferentes elementos e mesma de massa molecular.
Ex.: [C5H6O4]+; [C6H10O3]+, [C9H22]+ = 130 Da
Isótopos
São núcleos associados ao mesmo elemento da tabela periódica (mesmo númeroatômico) mas com diferentes números de nêutrons.
Ex: Hidrogênio, Deutério e Trítio
Isóbaros
São moléculas com diferentes elementos e mesma de massa molecular.
Ex.: [C5H6O4]+; [C6H10O3]+, [C9H22]+ = 130 Da
Isótopos
São núcleos associados ao mesmo elemento da tabela periódica (mesmo númeroatômico) mas com diferentes números de nêutrons.
Ex: Hidrogênio, Deutério e Trítio
Algumas definições importantesAlgumas definições importantes
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Elemento Isótopo Abund. Relativa Isótopo Abund. Relativa Isótopo Abund. RelativaCarbono 12C 100 13C 1.1Hidrogênio 1H 100 2H 0.016Nitrogêio 14N 100 15N 0.38Oxigênio 16O 100 17O 0.04 18O 0.2Enxoger 32S 100 33S 0.78 34S 4.4Cloro 35Cl 100 37 Cl 32.5Bromo 79Br 100 81Br 98
Espectro de Massas: ISÓTOPOS
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Espectro de Massas: abundância isotópica
Pico do Carbono 13Pico do Carbono 13
Pico monoisotópicoPico monoisotópico
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Espectro de Massas
m/z0 50 100 150 200 250
Ion
Abun
danc
e (%
)
0
20
40
60
80
100PrecursorPrecursor
FragmentosFragmentos
Espectro de dissociação/fragmentaçãoEspectro de dissociação/fragmentação
Íon molecular
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(mainlib) Benzoic acid, 2-hydroxy-, methyl ester10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
0
50
100
15
1828
39
4550
53
55
65
76 81
92
104 109
120
137
152
OH
O
O
(mainlib) Benzoic acid, 2-hydroxy-, methyl ester10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
0
50
100
15
1828
39
4550
53
55
65
76 81
92
104 109
120
137
152
OH
O
O
C7H6O3138.12
138.031694C 60.87% H 4.38% O 34.75%
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Espectro de Massas: abundância isotópicaPara se estimar o número de carbonos em uma molécula: dividir a intensidade de A+1 por 1.1 (abundância do Carbono 13 na natureza).
Para se estimar o número de carbonos em uma molécula: dividir a intensidade de A+1 por 1.1 (abundância do Carbono 13 na natureza).25%25%
25 / 1.1 = 23,7~ 23 átomos de
carbono na molécula
25 / 1.1 = 23,7~ 23 átomos de
carbono na molécula
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Espectro de Massas: abundância isotópica
Br - CH315 uma
79Br-CH3 = 9481Br-CH3 = 96
Informações:• Relação m/z• Presença dos isótopos• Diferença de massa entre os sinais
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Espectro de Massas: abundância isotópica
Cloro Peso atômico = 35,453Mistura de Cloro 35 (75,77%) e Cloro 37 (24,23%)
40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61mass0
100
%
7.49e1250.0
52.0
CH3Cl
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40 42 44 46 48 50 52 54 56 58 60mass0
100
%
50.0
52.0
Padrão isotópico: Cloro 35 (75,77%) e Cloro 37 (24,23%)
CH3Cl
74 76 78 80 82 84 86 88 90 92 94 96mass0
100
%
84.0
86.0
87.9
CH2Cl2
108 110 112 114 116 118 120 122 124 126 128 130 132mass0
100
%
117.9119.9
121.9
123.9
CHCl3
145 150 155 160 165mass0
100
%
153.9
151.9
155.9
157.9
CCl4
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Padrões isotópicos complexos
165 170 175 180 185 190mass0
100
%
3.06e12178.9436
172.9467
165 170 175 180 185 190mass0
100
%
3.06e12178.9436
172.9467
265 270 275 280 285 290mass0
100
%
1.52e12279.8496
265 270 275 280 285 290mass0
100
%
1.52e12279.8496
Composto contendo 1 átomo de RutênioComposto contendo 1 átomo de Rutênio
Composto contendo 2 átomo de RutênioComposto contendo 2 átomo de Rutênio
Evidência do número de elementos presentes na moléculaEvidência do número de elementos presentes na molécula
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Medida de Massa Molecular
Ex: M = 249C20H9+ C19H7N+ C13H19N3O2+
Ex: M = 249C20H9+ 249.0700C19H7N+ 249.0580C13H19N3O2+ 249.1479
Sistemas de Baixa resolução
Sistemas de Alta resolução
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MassaMassa nominalMassa de um íon de uma determinada fórmula empírica calculada através do isótopomais abundante.
Ex : M=249 C20H9+ or C19H7N+ or C13H19N3O2
+
Massa exataMassa de um íon da uma determinada fórmula empírica calculada através da massa exatado isótopo mais abaundante da cada elemento.
Ex : M=249 C20H9+ 249.070
C19H7N+ 249.0580C13H19N3O2
+ 249.1479
Faixa de massas- Limite superior e inferior de m/z observáveis por um dado analisador de massas.
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Resolução
Medida da habilidade de um analisador de massas de separar íons adjacentes.
249 249.0700 249.0580 249.1479
3 compostos diferentesMesma massa nominal
Baixa Resolução
3 compostos diferentes3 massas exatas diferentes
alta resolução
C20H9+C19H7N+
C13H19N3O2+ C20H9+ C19H7N+ C13H19N3O2+
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Massa Exata [C18H15P]+ m/z 262.0911
Massa exata (ppm)=106 (Mcal. – Mobs)/Mobs
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Caminhos de Fragmentação
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Possibilidades de EI
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Regra do Nitrogênio
• Contém Números ímpares de nitrogênio:
Íon molecular [M]+. terá massa ímpar!!
• Contém Números pares de átomos de Nitrogênio ou não contémátomos de nitrogênio:
Íon molecular [M]+. terá massa par!!
• Contém Números ímpares de nitrogênio:
Íon molecular [M]+. terá massa ímpar!!
• Contém Números pares de átomos de Nitrogênio ou não contémátomos de nitrogênio:
Íon molecular [M]+. terá massa par!!
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Regras do elétron impar
Regras do elétron par
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Fragmentação direcionada pelo elétron
Fragmentação direcionada pela carga
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Rearranjos