Universidade Federal de Uberlândia

Instituto de Biotecnologia
UFU
Laboratório de Biofisicoquímica LaBFiQ

das Moléculas
aos Tecidos

Professor Dr. Nilson Penha-Silva

Das Moléculas aos Tecidos
Cronograma de aulas da MEDUFU98
Sem Dia Data 08:00-08:50 08:50-09:40 09:50-10:40 10:40-11:30 13:10-14:00 14:00-14:50
Bioquímica: SP4:
Seg 16/05
Nilson Estudo Assíncrono
Histologia: Genética:
Ter 17/05
Letícia Aline
Histologia: Genética:
11ª Qua 18/05
Letícia Aline
Biofísica: Bioquímica: Bioquímica: Método:
Qui 19/05
Fábio Nilson Nilson Wallisen
SP4: Bioquímica:
Sex 20/05
Fechamento # 1 Nilson
Sab 21/05
Bioquímica: SP4:
Seg 23/05
Nilson Fechamento # 2
Anatomia: AT Genética:
Ter 24/05
Karina Aline
Histologia: Anatomia: APTA
12ª Qua 25/05
Letícia Karina
Biofísica: Bioquímica: Bioquímica: Método:
Qui 26/05
Fábio Nilson Nilson Wallisen
Bioquímica: Anatomia: APTB
Sex 27/05
Nilson Karina
Sab 28/05
 Universidade Federal de Uberlândia
Instituto de Biotecnologia
Laboratório de Biofisicoquímica
UFU LaBFiQ

Lipídeos:
Estruturas e Funções

Professor Dr. Nilson Penha-Silva

Lipídeos 4

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Lipídeos 5

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Ácidos graxos saturados 6

Nomenclatura, ponto de fusão e estado físico

Nº C Trivial Sistemática Estrutura PF (°C) Estado
C1 Ácido Fórmico Ácido Metanóico HCOOH 8.4
C2 Ácido Acético Ácido Etanóico CH3COOH 16.7
C3 Ácido Propiônico Ácido n-Propanóico CH3CH2COOH -22.0 Líquidos
C4 Ácido Butírico Ácido n-Butanóico CH3(CH2)2COOH -7.9 à temperatura
C6 Ácido Capróico Ácido n-Hexanóico CH3(CH2)4COOH -3.0 ambiente
C8 Ácido Caprílico Ácido n-Octanóico CH3(CH2)6COOH 16.7
C9 Ácido Pelargônico Ácido n-Nonanóico CH3(CH2)7COOH 12.5
C10 Ácido Cáprico Ácido n-Decanóico CH3(CH2)8COOH 29.6
C12 Ácido Láurico Ácido n-Dodecanóico CH3(CH2)10COOH 42.2
C14 Ácido Mirístico Ácido n-Tetradecanóico CH3(CH2)12COOH 52.1
C16 Ácido Palmítico Ácido n-Hexadecanóico CH3(CH2)14COOH 60.7
C18 Ácido Esteárico Ácido n-Octadecanóico CH3(CH2)16COOH 69.6 Sólidos
C20 Ácido Araquídico Ácido n-Eicosanóico CH3(CH2)18COOH 75.4 à temperatura
C22 Ácido Beênico Ácido n-Docosanóico CH3(CH2)20COOH 80.0 ambiente
C24 Ácido Lignocérico Ácido n-Tetracosanóico CH3(CH2)22COOH 84.2
C26 Ácido Cerótico Ácido n-Hexacosanóico CH3(CH2)24COOH 87.7
C28 Ácido Montânico Ácido n-Octacosanóico CH3(CH2)26COOH 90.9
 Ácidos graxos saturados
7

Conformação e ponto de fusão (69.6° C)

Stearic Acid, C18 Stearic Acid, C18

Source: Lehninger Principles of Biochemistry.

Ácidos graxos insaturados 8

Nomenclatura, representação esquemática e ponto de fusão

Nº C Trivial Sistemática Estrutura PF
(°C)
C16 Ácido Palmitoleico Ácido cis-9-Hexadecenóico 16:Δ9 1.0

C18 Ácido Elaídico Ácido trans-9-Octadecenóico 18:Δ9 45.0

C18 Ácido Oléico Ácido cis-9-Octadecenóico 18:Δ9 16.0

C18 Ácido Linoleico Ácido cis-cis-9,12-Ocatadecadienóico 18:Δ9,12 -5.0 Líquidos

à temperatura
C18 Ácido α-Linolênico Ácido cis,cis,cis-9,12,15-Octadecatrienóico 18:Δ9,12,15 -11.0 ambiente

C18 Ácido γ-Linolênico Ácido cis,cis,cis-6,9,12-Ocatadecatrienóico 18:Δ6,9,12 -11.3

Duplas
C18 Ácido -Eleosteárico Ácido cis,trans,trans-9,11,13-Octadecatrienóico 18:Δ9,11,13 48.0 conjugadas

C20 Ácido Araquidônico Ácido cis,cis,cis,cis-5,8,11,14-Eicosatetraenóico 20:Δ5,8,11,14 - 49.5

C20 Ácido Clupanodônico Ácido cis,cis,cis,cis,cis-5,8,11,14,17-Eicosapentaenóico 20:Δ5,8,11,14,17 - 78.0

C24 Ácido Nervônico Ácido cis-15-Tetracosenóico 24:Δ15 42.5

Ácidos graxos insaturados 9

Influência da configuração da dupla ligação no ponto de fusão

Nº C Trivial Sistemática Estrutura PF
(°C)
C16 Ácido Palmitoleico Ácido cis-9-Hexadecenóico 16:Δ9 1.0

C18 Ácido Elaídico Ácido trans-9-Octadecenóico 18:Δ9 45.0

C18 Ácido Oléico Ácido cis-9-Octadecenóico 18:Δ9 16.0

C18 Ácido Linoleico Ácido cis-cis-9,12-Ocatadecadienóico 18:Δ9,12 -5.0 Líquidos

à temperatura
C18 Ácido α-Linolênico Ácido cis,cis,cis-9,12,15-Octadecatrienóico 18:Δ9,12,15 -11.0 ambiente

C18 Ácido γ-Linolênico Ácido cis,cis,cis-6,9,12-Ocatadecatrienóico 18:Δ6,9,12 -11.3

Duplas
Duplas
C18 Ácido -Eleosteárico Ácido cis,trans,trans-9,11,13-Octadecatrienóico 18:Δ9,11,13 48.0 conjugadas
conjugadas

C20 Ácido Araquidônico Ácido cis,cis,cis,cis-5,8,11,14-Eicosatetraenóico 20:Δ5,8,11,14 - 49.5

C20 Ácido Clupanodônico Ácido cis,cis,cis,cis,cis-5,8,11,14,17-Eicosapentaenóico 20:Δ5,8,11,14,17 - 78.0

C24 Ácido Nervônico Ácido cis-15-Tetracosenóico 24:Δ15 42.5

Ácidos graxos insaturados trans-configurados
10

Configuração da dupla ligação, conformação e ponto de fusão

Oleic Acid, 18:cis-Δ9, 9

Elaidic Acid, 18:trans-Δ9, 9

Elaidic Acid, 18:trans-Δ9, 9

Source: Penha-Silva N. Personal Bank of Images.

Ácido -eleoesteárico (cis,trans,trans-9,11,13-octadecatrienóico)
Configuração da dupla ligação, conformação e ponto de fusão

(três duplas ligações conjugadas, duas trans configuradas)

Ácidos graxos insaturados 12

Influência do número de duplas ligações cis-configuradas

Nº C Trivial Sistemática Estrutura PF
(°C)
C16 Ácido Palmitoleico Ácido cis-9-Hexadecenóico 16:Δ9 1.0

C18 Ácido Elaídico Ácido trans-9-Octadecenóico 18:Δ9 45.0

C18 Ácido Oléico Ácido cis-9-Octadecenóico 18:Δ9 16.0

C18 Ácido Linoleico Ácido cis-cis-9,12-Ocatadecadienóico 18:Δ9,12 -5.0 Líquidos

à temperatura
C18 Ácido α-Linolênico Ácido cis,cis,cis-9,12,15-Octadecatrienóico 18:Δ9,12,15 -11.0 ambiente

C18 Ácido γ-Linolênico Ácido cis,cis,cis-6,9,12-Ocatadecatrienóico 18:Δ6,9,12 -11.3

C18 Ácido -Eleosteárico Ácido cis,trans,trans-9,11,13-Octadecatrienóico 18:Δ9,11,13 48.0

C20 Ácido Araquidônico Ácido cis,cis,cis,cis-5,8,11,14-Eicosatetraenóico 20:Δ5,8,11,14 - 49.5

C20 Ácido Clupanodônico Ácido cis,cis,cis,cis,cis-5,8,11,14,17-Eicosapentaenóico 20:Δ5,8,11,14,17 - 78.0

C24 Ácido Nervônico Ácido cis-15-Tetracosenóico 24:Δ15 42.5

Ácidos graxos insaturados cis-configurados
13

Duplas ligações cis-configuradas, conformação e ponto de fusão

Oleic Acid, 18:cis-Δ9, 9 Oleic Acid, 18: cis-Δ9, 9

Source: Lehninger Principles of Biochemistry.

Ácidos graxos insaturados 14

Nomenclatura
Nº C Trivial Sistemática Estrutura PF
(°C)
C16 Ácido Palmitoleico Ácido cis-9-Hexadecenóico 16:Δ9 1.0

C18 Ácido Elaídico Ácido trans-9-Octadecenóico 18:Δ9 45.0

C18 Ácido Oléico Ácido cis-9-Octadecenóico 18:Δ9 16.0

C18 Ácido Linoleico Ácido cis-cis-9,12-Ocatadecadienóico 18:Δ9,12 -5.0 Líquidos

à temperatura
C18 Ácido α-Linolênico Ácido cis,cis,cis-9,12,15-Octadecatrienóico 18:Δ9,12,15 -11.0 ambiente

C18 Ácido γ-Linolênico Ácido cis,cis,cis-6,9,12-Ocatadecatrienóico 18:Δ6,9,12 -11.3

C18 Ácido -Eleosteárico Ácido cis,trans,trans-9,11,13-Octadecatrienóico 18:Δ9,11,13 48.0

C20 Ácido Araquidônico Ácido cis,cis,cis,cis-5,8,11,14-Eicosatetraenóico 20:Δ5,8,11,14 - 49.5

C20 Ácido Clupanodônico Ácido cis,cis,cis,cis,cis-5,8,11,14,17-Eicosapentaenóico 20:Δ5,8,11,14,17 - 78.0

C24 Ácido Nervônico Ácido cis-15-Tetracosenóico 24:Δ15 42.5

Ácido cis,cis,cis,cis,cis-5,8,11,14,17-Eicosapentaenóico
15

Número de duplas cis-configuradas, conformação e ponto de fusão

Ácidos graxos polinsaturados 16

Lipoperoxidação

Source: Marks's Basic Medical Biochemistry..

Ácidos graxos polinsaturados
17

Lipoperoxidação

Fatty acid free radical

•

Source: Marks's Basic Medical Biochemistry. Mod.

Peroxyl free radical
I
O
I
O
•
Hydroperoxide
I
O
I
O
I
H
 Iniciação e propagação

or
Lipoperoxidação de PUFA

O2
18

Source: Juan et al. Int. J. Mol. Sci. 2021, 22(9), 4642.

Lipoperoxidação de ácidos graxos polinsaturados
19

Lipoperoxidação de um éster de ácido araquidônico

Source: Juan et al. Int. J. Mol. Sci. 2021, 22(9), 4642.

 20
Óleos e gorduras
Composição em ácidos graxos (%) de óleos e gorduras
Fonte Saturados Insaturados
C4-C12 C14 C16 C18 C16 + C18
Canola - - 5 1 94
Girassol - - 6 3 91
Milho - 2 10 3 85
Soja - 2 10 3 85
Amendoim - 5 8 3 84
Oliva 2 2 13 3 80
Carne bovina 2 2 29 21 46
Manteiga 10 11 29 10 40
Coco 60 18 11 2 8
Noz moscada 7 90 3 - --
 21
Gorduras animais
Composição em ácidos graxos (%) de gorduras animais
Tecido adiposo Fígado Leite
Humano Bovino Suíno Ovino Bovino Vaca
Butírico 9
Capróico 3
Caprílico 2
Cáprico 4
Láurico 3
Mirístico 3 7 1 2 3 11
Palmítico 23 29 28 25 35 23
Esteárico 6 21 10 26 5 9
Palmitoléico 5 10 4
Oléico 50 41 58 42 36 26
Linoléico 10 2 3 5 8 3
C20-22 insaturado 3
The Lancet, Published: 29 August 2017, DOI: http://dx.doi.org/10.1016/S0140-6736(17)32252-3

Associations of fats and carbohydrate intake with cardiovascular disease and mortality in 18 countries from five continents
(PURE): a prospective cohort study
Dehghan, M. et al.
Background The relationship between macronutrients and cardiovascular disease and mortality is controversial. Most available data are
from European and North American populations where nutrition excess is more likely, so their applicability to other populations is
unclear. Methods The Prospective Urban Rural Epidemiology (PURE) study is a large, epidemiological cohort study of individuals aged
35–70 years (enrolled between Jan 1, 2003, and March 31, 2013) in 18 countries with a median follow-up of 7·4 years (IQR 5·3–9·3).
Dietary intake of 135 335 individuals was recorded using validated food frequency questionnaires. The primary outcomes were total
mortality and major cardiovascular events (fatal cardiovascular disease, non-fatal myocardial infarction, stroke, and heart failure).
Secondary outcomes were all myocardial infarctions, stroke, cardiovascular disease mortality, and non-cardiovascular disease mortality.
Participants were categorised into quintiles of nutrient intake (carbohydrate, fats, and protein) based on percentage of energy provided
by nutrients. We assessed the associations between consumption of carbohydrate, total fat, and each type of fat with cardiovascular
disease and total mortality. We calculated hazard ratios (HRs) using a multivariable Cox frailty model with random intercepts to account
for centre clustering. Findings During follow-up, we documented 5796 deaths and 4784 major cardiovascular disease events. Higher
carbohydrate intake was associated with an increased risk of total mortality (highest [quintile 5] vs lowest quintile [quintile 1] category,
HR 1·28 [95% CI 1·12–1·46], ptrend=0·0001) but not with the risk of cardiovascular disease or cardiovascular disease mortality. Intake of
total fat and each type of fat was associated with lower risk of total mortality (quintile 5 vs quintile 1, total fat: HR 0·77 [95% CI 0·67–
0·87], ptrend<0·0001; saturated fat, HR 0·86 [0·76–0·99], ptrend=0·0088; monounsaturated fat: HR 0·81 [0·71–0·92], ptrend<0·0001; and
polyunsaturated fat: HR 0·80 [0·71–0·89], ptrend<0·0001). Higher saturated fat intake was associated with lower risk of stroke (quintile
5 vs quintile 1, HR 0·79 [95% CI 0·64–0·98], ptrend=0·0498). Total fat and saturated and unsaturated fats were not significantly associated
with risk of myocardial infarction or cardiovascular disease mortality. Interpretation High carbohydrate intake was associated with
higher risk of total mortality, whereas total fat and individual types of fat were related to lower total mortality. Total fat and
types of fat were not associated with cardiovascular disease, myocardial infarction, or cardiovascular disease mortality,
whereas saturated fat had an inverse association with stroke. Global dietary guidelines should be reconsidered in light of these
findings.
 BMJ. 2015 Aug 11;351:h3978. doi: 10.1136/bmj.h3978. 23
Intake of saturated and trans unsaturated fatty acids and risk of all cause mortality, cardiovascular disease, and type 2 diabetes:
systematic review and meta-analysis of observational studies
de Souza RJ1, Mente A2, Maroleanu A3, Cozma AI4, Ha V5, Kishibe T6, Uleryk E7, Budylowski P8, Schünemann H9, Beyene J10, Anand SS11
McMaster University, Hamilton, ON, Canada
OBJECTIVE: To systematically review associations between intake of saturated fat and trans unsaturated fat and all cause mortality, cardiovascular
disease (CVD) and associated mortality, coronary heart disease (CHD) and associated mortality, ischemic stroke, and type 2 diabetes. DESIGN:
Systematic review and meta-analysis. DATA SOURCES: Medline, Embase, Cochrane Central Registry of Controlled Trials, Evidence-Based Medicine
Reviews, and CINAHL from inception to 1 May 2015, supplemented by bibliographies of retrieved articles and previous reviews. ELIGIBILITY
CRITERIA FOR SELECTING STUDIES: Observational studies reporting associations of saturated fat and/or trans unsaturated fat (total, industrially
manufactured, or from ruminant animals) with all cause mortality, CHD/CVD mortality, total CHD, ischemic stroke, or type 2 diabetes. DATA
EXTRACTION AND SYNTHESIS: Two reviewers independently extracted data and assessed study risks of bias. Multivariable relative risks were
pooled. Heterogeneity was assessed and quantified. Potential publication bias was assessed and subgroup analyses were undertaken. The GRADE
approach was used to evaluate quality of evidence and certainty of conclusions. RESULTS: For saturated fat, three to 12 prospective cohort
studies for each association were pooled (five to 17 comparisons with 90 501-339 090 participants). Saturated fat intake was not associated with
all cause mortality (relative risk 0.99, 95% confidence interval 0.91 to 1.09), CVD mortality (0.97, 0.84 to 1.12), total CHD (1.06, 0.95 to 1.17),
ischemic stroke (1.02, 0.90 to 1.15), or type 2 diabetes (0.95, 0.88 to 1.03). There was no convincing lack of association between saturated fat and
CHD mortality (1.15, 0.97 to 1.36; P=0.10). For trans fats, one to six prospective cohort studies for each association were pooled (two to seven
comparisons with 12 942-230 135 participants). Total trans fat intake was associated with all cause mortality (1.34, 1.16 to 1.56), CHD mortality
(1.28, 1.09 to 1.50), and total CHD (1.21, 1.10 to 1.33) but not ischemic stroke (1.07, 0.88 to 1.28) or type 2 diabetes (1.10, 0.95 to 1.27). Industrial,
but not ruminant, trans fats were associated with CHD mortality (1.18 (1.04 to 1.33) v 1.01 (0.71 to 1.43)) and CHD (1.42 (1.05 to 1.92) v 0.93 (0.73
to 1.18)). Ruminant trans-palmitoleic acid was inversely associated with type 2 diabetes (0.58, 0.46 to 0.74). The certainty of associations between
saturated fat and all outcomes was "very low." The certainty of associations of trans fat with CHD outcomes was "moderate" and "very low" to
"low" for other associations. CONCLUSIONS: Saturated fats are not associated with all causes of mortality, CVD, CHD, ischemic stroke, or
type 2 diabetes, but the evidence is heterogeneous with methodological limitations. Trans fats are associated with all causes of
mortality, total CHD, and CHD mortality, probably because of higher levels of intake of industrial trans fats than ruminant trans fats.
Dietary guidelines must carefully consider the health effects of recommendations for alternative macronutrients to replace trans fats and
saturated fats.
 24

CVD, cardiovascular disease

CHD, coronary heart disease Heterogeneity analysis, Cochran’s Q test
CVD, cardiovascular disease
CHD, coronary heart disease Heterogeneity analysis, Cochran’s Q test
 Inform, American Oil Chemists’ Society, 25 (10), pp. 614-624, 2014 26

Detection, monitoring, and deleterious health effects of lipid oxidation products

generated in culinary oils during thermal stressing episodes

Martin Grootveld, Victor Ruiz Rodado, and Christopher J.L. Silwood

School of Pharmacy, De Montfort University, The Gateway, Leicester, LE1 9BH

Trans fatty acids have received considerable attention in the media and the scientific literature
(together with their putative atherogenic and carcinogenic actions). The far more toxic
aldehydes generated in thermally stressed culinary oils, however, have received little or none.
The most important chemical reaction involved is the self-sustaining, free radical-
mediated oxidative deterioration of polyunsaturated fatty acids (PUFAs), which occurs
during the heating of culinary oils and, to a much diminished level, saturated fatty acid (SFA)-
rich fats. This oxidative degradation process can generate extremely toxic conjugated lipid
hydroperoxydienes (CHPDs). These are unstable at standard frying temperatures (ca. 180°C)
and are degraded to a broad range of secondary products, particularly saturated and
unsaturated aldehydes, together with di- and epoxyaldehydes. Such aldehydic fragments also
have toxicological properties in humans owing to their high reactivity with critical
biomolecules in vivo (proteins such as low-density lipoprotein, amino acids, thiols such as
glutathione, DNA, etc.). Despite their reactivities, high levels of CHPDs can remain in PUFA-
rich oils which have been subjected to routine frying practices.
Lipídeos
27

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Lipídeos
28

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Lipídeos
29

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Lipídeos
30

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Acilgliceróis
31

Conceito
Acilgliceróis
32

Classificação

Monoacilglicerol Diacilglicerol Triacilglicerol

Acilgliceróis
33

Hidrólise alcalina: Saponificação

Triacilglicerol Glicerol Sabões

Acilgliceróis
34

Hidrólise enzimática: Digestão e rancificação hidrolítica

Triacilglicerol Glicerol Ácidos Graxos

Lipídeos 35

Rancificação oxidativa de ácidos graxos polinsaturados

Fatty acid free radical

•

Source: Marks's Basic Medical Biochemistry. Mod.

Peroxyl free radical
I
O
I
O
•
Hydroperoxide
I
O
I
O
I
H
Lipídeos
36

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Fosfoacilgliceróis 37

Conceito

Glicerol-fosfato
Fosfoacilgliceróis
38

Conceito
Lipídeos
39

Classificação

• Ácidos graxos livres

• Ésteres do glicerol
– Acilgliceróis Fosfatidatos
Plasmalogênios
– Fosfoacilgliceróis Fosfoinositídeos
Difosfatidilgliceróis
• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Fosfoacilgliceróis
40

1) Fosfatidatos

Source: Smith, E. et al. Bioquímica: Aspectos Gerais.

Ácido fosfatídico Fosfatidil-etanolamina
(Cefalina)

+ +

Fosfatidil-serina Fosfatidil-colina
(Lecitina)
Prelúdio de uma tragédia
Sugestões de leitura

Resenha: https://pt.wikipedia.org/wiki/Fosfoetanolamina
Resenha: https://revistaquestaodeciencia.com.br/resenha/2019/11/01/saga-da-fosfo-mistura-teoria-da-conspiracao-e-ciencia-ruim
A minuta do projeto de lei: https://www.camara.leg.br/proposicoesWeb/prop_mostrarintegra?codteor=1440430 (2016)
Repercussão: Escobar, Herton. Brazil bill would legalize renegade cancer pill. Science, Vol. 352, Ed. 6281, pp. 18 - DOI: 10.1126/science.352.6281.18 (2016)
A derrubada da lei: https://g1.globo.com/politica/noticia/2020/10/26/fosfoetanolamina-stf-declara-inconstitucional-lei-que-liberava-pilula-do-cancer.ghtml
FASEB J. 1991 Apr;5(7):2093-8
Choline, an essential nutrient for humans

S H Zeisel 1, K A Da Costa, P D Franklin, E A Alexander, J T Lamont, N F Sheard, A Beiser

1Department of Nutrition, University of North Carolina, Chapel Hill 27599-7400.

Choline is required to make essential membrane phospholipids. It is a precursor for the biosynthesis of the
neurotransmitter acetylcholine and also is an important source of labile methyl groups. Mammals fed a choline-
deficient diet develop liver dysfunction; however, choline is not considered an essential nutrient in humans. Healthy
male volunteers were hospitalized and fed a semisynthetic diet devoid of choline supplemented with 500 mg/day
choline for 1 wk. Subjects were randomly divided into two groups, one that continued to receive choline (control), and
the other that received no choline (deficient) for three additional wk. During the 5th wk of the study all subjects
received choline. The semisynthetic diet contained adequate, but no excess, methionine. In the choline-deficient group,
plasma choline and phosphatidylcholine concentrations decreased an average of 30% during the 3-wk period when a
choline-deficient diet was ingested; plasma and erthrocyte phosphatidylcholine decreased 15%; no such changes
occurred in the control group. In the choline-deficient group, serum alanine aminotransferase activity increased
steadily from a mean of 0.42 μkatal/L to a mean of 0.62 μkatal/L during the 3-wk period when a choline-deficient diet
was ingested; no such change occurred in the control group. Other tests of liver and renal function were unchanged in
both groups during the study. Serum cholesterol decreased an average of 15% in the deficient group and did not
change in the control group. Healthy humans consuming a choline-deficient diet for 3 wk had depleted stores of
choline in tissues and developed signs of incipient liver dysfunction. Our observations support the conclusion and
choline is an essential nutrient for humans when excess methionine and folate are not available in the diet.
Fatores nutricionais essenciais 43

Lipídeos
Água Vitaminas hidrossolúveis Ácido ascórbico (C)
Ácido fólico (B9)
Oxigênio
Ácido pantotênico
Aminoácidos Arginina Biotina
Fenilalanina Cobalamina (B12)
Histidina Colina
Isoleucina Niacina
Piridoxina (B6)
Leucina
Riboflavina (B2)
Lisina Tiamina (B1)
Metionina
Macrominerais Cálcio
Treonina
Cloreto
Triptofano Fosfato
Valina Magnésio
Carboidratos Potássio
Sódio
Lipídeos Ácido linoléico
Microminerais Cobre
Ácido α-linolênico
Cromo
Fibras Ferro
Iodo
Vitaminas lipossolúveis A Manganês
D Molibdênio
E Selênio
K Zinco
 2) Plasmalogênios
Fosfoacilgliceróis
44

Source: Smith, E. et al. Bioquímica: Aspectos Gerais.

 Fosfoacilgliceróis
3) Difosfatidilgliceróis
45

Source: Smith, E. et al. Bioquímica: Aspectos Gerais.

 4) Fosfoinositídeos
Fosfoacilgliceróis
46

Source: Smith, E. et al. Bioquímica: Aspectos Gerais.

 47

Source: Rodwell et al. Harper’s Illustrated Biochemistry. Mod.

Anfifílicos de membrana

Phospholipase C
2 DAG plus IP3
(+)
Adrenaline

Phosphoinositide
Transdução de sinais

1
Adrenaline
Angiotensin II (+) Phospholipase A2 (−) Anti-inflammatory corticosteroids
Thrombin

Arachidonic Acid
Aspirin
LOx COx (−)
Indomethacin

Leukotrienes Prostaglandins
Lipoxins Thromboxanes
Lipídeos
48

Classificação

• Ácidos graxos livres

• Ésteres de glicerol
– Acilgliceróis
– Fosfoacilgliceróis

• Lipídeos que não são ésteres de glicerol

• Lipoconjugados
– Glicolipídeos
– Lipoproteínas
Lipídeos
49

Classificação

• Ácidos graxos livres

• Ésteres de glicerol
– Acilgliceróis
– Fosfoacilgliceróis ▪ Álcoois alifáticos
▪ Ceras
▪ Terpenos
• Lipídeos que não são ésteres de glicerol ▪ Esteroides
▪ Eicosanóides
• Lipoconjugados ▪ Esfingolipídeos
– Glicolipídeos
– Lipoproteínas
Lipídeos que não são ésteres de glicerol 50

1) Álcoois alifáticos

CH3(CH2)28CH2OH

Source: Lehninger Principles of Biochemistry.

1-Triacontanol (álcool miricílico)
Lipídeos que não são ésteres de glicerol
51

A cera de abelha é um produto heterogêneo

Source: Lehninger Principles of Biochemistry.

J. Am. Acad. Dermatol. 1990 Nov;23(5 Pt 1):845-9. doi: 10.1016/0190-9622(90)70301-w.
Composition of cerumen lipids
J T Bortz 1, P W Wertz, D T Downing
1Marshall Dermatology Research Laboratories, Department of Dermatology, University of Iowa College of Medicine, Iowa City 52242.

Lipids were extracted from "wet" cerumen and analyzed by quantitative thin-layer
chromatography to determine their composition. The lipid fraction comprised 52% of the dry
weight of cerumen and consisted of squalene (6.4%), cholesterol esters (9.6%), wax esters
(9.3%), triacylglycerols (3.0%), fatty acids (22.7%), cholesterol (20.9%), ceramides (18.6%),
cholesterol sulfate (2.0%), and several unidentified polar components (7.5%). In addition to
the extractable lipids, the residue contained an additional 0.9% lipid that could be released only
after saponification. This covalently bound lipid consisted of two unusual ceramides (63.4%),
omega-hydroxyacids (27.7%) and nonhydroxy fatty acids (8.8%). The composition of this bound
lipid resembled that recently found in human stratum corneum, which is thought to comprise a
lipid envelope on the outer surface of the corneocytes. The free and covalently bound lipids may
be significant determinants of the properties of cerumen. Desquamation of corneocytes
[terminally differentiated keratinocytes that compose most the stratum corneum, the outermost
part of the epidermis] and their associated lipids from the epidermal lining of the ear canal may
make a major contribution to cerumen.
Lipídeos que não são ésteres de glicerol
53

3) Terpenos

Source: Lehninger Principles of Biochemistry.

(2-metil-butadieno)
Lipídeos que não são ésteres de glicerol
54

3) Terpenos: a ubiquinona

Source: Lehninger Principles of Biochemistry.

Ubiquinone
(Coenzyme Q),
a mitochondrial electron carrier
Lipídeos que não são ésteres de glicerol
55

3) Terpenos: a plastoquinona

Source: Lehninger Principles of Biochemistry.

Plastoquinone,
a chloroplast electron carrier
Lipídeos que não são ésteres de glicerol
56

3) Terpenos: a vitamina E

Source: Lehninger Principles of Biochemistry. Mod.

α-Tocopherol
(Vitamin E),
an anti-oxidant compound.
Vitamina E
A vitamina E compreende um grupo de oito diferentes compostos

Etsuo Niki and Kouichi Abe, CHAPTER 1: Vitamin E: Structure, Properties and Functions , in Vitamin E: Chemistry and Nutritional Benefits, 2019, pp. 1-11
DOI: 10.1039/9781788016216-00001.
Lipídeos que não são ésteres de glicerol
58

3) Terpenos: a vitamina K

Source: Lehninger Principles of Biochemistry. Mod.

Phylloquinone
(Vitamin K1),
a blood-clotting compound.
Vitamina K
A vitamina K compreende diferentes compostos
1 2 3 4 5 6 7

Phylloquinone (Vitamin K1)

Menaquinone-4 (Vitamin K2)

Menaquinone-7 (Vitamin K2)

Turck, Dominique et al. (2017). Dietary reference values for vitamin K. EFSA Journal. 15. DOI: 10.2903/j.efsa.2017.4780.