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IMPORTANCIA DE LAS GRASAS EN LA ALIMENTACIN

Rosa M. Ortega
Departamento de Nutricin. Facultad de Farmacia. Universidad Complutense.
Madrid.
El descubrimiento de la importancia de los lpidos en una nutricin sana es un proceso que se
inici a partir de los aos veinte. Anteriormente se crea que la grasa no desempeaba un
papel esencial en laalimentacin si se consuman cantidades suficientes de vitaminas y
minerales con la dieta. Sin embargo, Aron propuso en 1918 (1) que la grasa tena un valor
nutritivo que no poda ser suplido por otros componentes de los alimentos. Posteriormente,
Burr y Burr (2) documentaron la existencia de una sustancia esencial en lagrasa: el cido
linoleico (C18:2 n-6), sealando que en ausencia de este nutriente se desarrollan sntomas
que afectan a la salud de la piel, retencin de agua, fertilidad y crecimiento (2,3).
Posteriormente, se prest atencin a la relacin existente entre cantidad y tipo
de grasa consumida y el riesgo de sufrir enfermedades cardiovasculares, cncer y otras
enfermedades degenerativas. El mensaje principal que result de estos estudios llev a
aconsejar moderacin en el consumo de grasa total, grasa saturada y colesterol. En los
ltimos 10 aos muchas fracciones lipdicas han recibido atencin al comprobarse su
importancia en la disminucin de riesgo de diversas patologas y deterioros. Las
investigaciones realizadas y el desarrollo de alimentos enriquecidos con estas fracciones
lipdicas (cidos grasos omega-3 [w-3], esteroles vegetales...) abren nuevos caminos en la
bsqueda de una mejora de la salud y calidad de vida, por modificacin en el consumo
de grasas.
CONCEPTO, CLASIFICACIN, ASPECTOS QUMICOS
Las grasas son un conjunto heterogneo de sustancias que tienen en comn su insolubilidad
en agua y su solubilidad en solventes orgnicos (como ter o cloroformo). Se encuentran en
todas las clulas (animales y vegetales) y se pueden sintetizar a partir de los hidratos de
carbono (4,5).
Como el resto de los macronutrientes, las sustancias lipdicas contienen los tres elementos:
carbono, hidrgeno y oxgeno. Por tener mayor cantidad de carbono e hidrgeno,
la grasa libera ms energa; en concreto, su oxidacin produce 2,25 veces, o ms, energa
por unidad de peso, en comparacin con la obtenida a partir de carbohidratos y protenas;
por ello, este macronutriente es la fuente ms concentrada de energa y proporciona
aproximadamente 9 kcal/g (3-5).
Las grasas a temperatura ambiente son slidas, debido a que en su estructura predominan
los cidos grasos saturados. Sin embargo, los aceites, al tener una mayor proporcin
de cidos grasos insaturados, son lquidos a temperatura ambiente. La grasa se denomina
visible cuando puede ser aadida voluntariamente (margarina, mantequilla, aceite...) y no
visible cuando forma parte de tejidos o de otros componentes de los alimentos (6). Aunque el
trmino grasa hace referencia a numerosas sustancias, desde el punto de vista de la
alimentacin merecen atencin:
1. Los triglicridos (lpidos simples).
2. Los fosfolpidos (lpidos complejos).
3. Otros lpidos (esteroles y vitaminas liposolubles).
Lpidos simples
Incluyen los cidos grasos y los steres de cidos grasos con glicerol (monoglicridos,
diglicridos, triglicridos). De ellos, los triglicridos son los que merecen mayor atencin por
su importancia y abundancia. Los triglicridos estn formados por una molcula de glicerol
(alcohol soluble en agua) y tres molculas decidos grasos unidos por uniones de tipo ster
(figura 1).

Fig. 1. Estructura de un triglicrido y un fosfolpido

Los cidos grasos desempean un importante papel en las grasas, dado que forman parte de
lostriglicridos (en los que se unen al glicerol), pero tambin de los fosfolpidos (junto con
glicerol, grupo fosfato y otros grupos hidroflicos); adems, pueden esterificarse con
el colesterol (para dar lugar a steres del colesterol). Los cidos grasos de inters biolgico
son cidos carboxlicos con un nmero de tomos de carbono par (entre 4 y 24) y se pueden
clasificar por la longitud de su cadena, su estructura y posicin del primer doble enlace (4,7).
Por la longitud de su cadena, pueden ser de cadena corta (4-6 carbonos), de cadena media
(8-12 carbonos), de cadena larga (14-18 carbonos) y de cadena muy larga (20 o ms
carbonos). Teniendo en cuenta su estructura qumica, se clasifican en:
cidos grasos saturados (AGS): sin dobles enlaces (todos los enlaces de la molcula son
sencillos).
cidos grasos monoinsaturados (AGM): con un doble enlace.
cidos grasos poliinsaturados (AGP): con ms de un doble enlace.
Por su configuracin espacial, puede haber cidos grasos cis o trans. Los dobles enlaces casi
siempre tienen una configuracin cis, lo que origina un ngulo de unos 120 y una curvatura
de la molcula. Sin embargo, los cidos grasos trans, que se encuentran de manera natural,
en pequeas cantidades, en la grasa de la leche y carne de los rumiantes y se producen a
escala industrial en algunos procesos de hidrogenacin, refinado, etc., son rectos como los
saturados y tienen propiedades biolgicas diferentes de los cis; en concreto, se pueden
acumular en algunos tejidos y provocar alteraciones tisulares. Tambin tienen un efecto
hipercolesterolmico (7,8).
La posicin del primer doble enlace tambin tiene importancia fisiolgica y ha llevado a
definir tres series de cidos grasos: los n-3, cuando el primer doble enlace se encuentra en la
posicin 3 desde el metilo terminal, y los n-6 y n-9, cuando este doble enlace est en
posicin 6 o 9 a partir del carbono terminal, respectivamente. Las series n-3, n-6 y n-9
(tambin denominadas w-3, w-6 y w-9) definen grupos de cidos grasos, relacionados
metablicamente, que tienen en comn la posicin del primer doble enlace a partir del
extremo metilo (4,8).
Los cidos grasos tienen un nombre comn y otro sistemtico y se suelen denominar
tambin indicando el nmero de carbonos, los dobles enlaces que presentan y la posicin del
primero de ellos (tablas 1 y 2).
Tabla 1. cidos grasos de mayor inters nutricional

Tabla 2. cidos grasos e interrelaciones entre ellos (5)

Por la accin de desaturasas y elongasas, los cidos grasos de las series omega-3, omega6 y omega-9permiten la obtencin de derivados de inters biolgico. Concretamente, a partir
del cido alfa-linolnico(omega-3) se pueden obtener los cidos eicosapentaenoico (EPA) y
docosahexaenoico (DHA); a partir delcido linoleico (omega-6) se obtiene el cido
araquidnico, y del cido oleico (omega-9) se sintetizan, entre otros, el cido
eicosatrienoico5. Sin embargo, el cido linoleico utiliza las mismas enzimas para
desaturacin y elongacin que el alfa-linolnico, por lo que un exceso en su aporte puede
limitar la sntesis de EPA y DHA, lo que no resulta conveniente (9).
Lpidos complejos
Los lpidos complejos tienen poca importancia en relacin con su aporte diettico, pero
realizan funciones estructurales y fisiolgicas vitales en el organismo; concretamente, forman
parte de membranas, cuya actividad modulan, y se utilizan en la construccin de compuestos

de gran actividad biolgica: los eicosanoides (6,10). Entre ellos, los fosfolpidos son los que se
pueden encontrar en la dieta (en alimentos como hgado, sesos, corazn y yema de huevo) y
comercialmente se utilizan bastante como emulsionantes en la fabricacin de margarinas y
quesos (6). Los fosfolpidos, como su nombre indica, son lpidos que incluyen cido fosfrico
en su composicin. Entre ellos, los fosfoglicridos incluyen glicerol, esterificado en los
carbonos 1 y 2 con dos cidos grasos y en el carbono 3 por cido fosfrico (6) (figura 1). Si el
cido fosfrico se une a la colina, se obtiene la fosfatidilcolina (lecitina), mientras que la
fosfatidilserina y fosfatidiletanolamina se obtienen por unin del cido fosfrico con serina y
etanolamina, respectivamente. Estos fosfoglicridos son los tres fosfolpidos ms abundantes
en el organismo y forman parte de membranas celulares, constituyendo una bicapa con los
extremos hidrocarbonados dirigidos hacia el interior de la membrana y las cabezas polares
hacia el exterior y el interior de la clula. Hay otros fosfolpidos, como las esfingomielinas,
que forman parte de la estructura de las vainas de mielina de las neuronas (6,10).
Otros lpidos
Incluyen las vitaminas liposolubles y los esteroles (colesterol y esteroles
vegetales o fitosteroles). Elcolesterol est constituido por una estructura bsica formada por
4 anillos y una cadena hidrocarbonada ramificada de 8 tomos de carbono (figura 2); forma
steres con distintos cidos grasos y es as como se ingiere con los alimentos (6).

Fig. 2
El colesterol forma parte de la estructura de membranas celulares y es el precursor de
molculas de gran importancia biolgica, como hormonas esteroideas, vitamina D y cidos
biliares. Slo los alimentos de origen animal proporcionan colesterol, pero el organismo
tambin puede sintetizarlo en diversos tejidos (especialmente en el hgado) a partir de
acetato (6,10).
Las grasas que derivan de los vegetales tienen esteroles vegetales o fitosteroles, compuestos
estructuralmente relacionados con el colesterol (figura 2). Los fitosteroles ms comunes son
betasitosterol, campesterol y estigmasterol; en contraste con el colesterol, estos esteroles se
absorben en muy pequea proporcin (0-10% en funcin del esterol vegetal concreto); por
otra parte, su presencia interfiere con la incorporacin del colesterol en las micelas
intestinales, lo que contribuye a disminuir su absorcin (5,7).
FUNCIONES DE LAS GRASAS EN EL ORGANISMO
Las grasas proporcionan al organismo energa y cidos grasos esenciales y, adems, realizan
funciones estructurales y reguladoras (3).

Energa
Las clulas del cuerpo, excepto las del sistema nervioso central y los
glbulos rojos, pueden utilizar cidos grasos directamente como fuente de
energa. El cerebro, aunque normalmente emplea carbohidratos, tambin es
capaz de utilizar cuerpos cetnicos, que se forman a partir de los cidos
grasos durante los periodos de ayuno (3).

Las grasas pueden ser fuente de energa inmediata (por combustin de los cidos
grasos libres en la circulacin, en el proceso de betaoxidacin) o servir como un reservorio de
energa para cubrir las necesidades a ms largo plazo. De hecho, mientras que el cuerpo
acumula cantidades pequeas o limitadas de protenas y de carbohidratos, almacena la
mayor parte del exceso de energa en forma de triglicridos en las clulas del tejido adiposo
(3). Este almacn est continuamente renovndose con el control de la hormona del
crecimiento, insulina, epinefrina, ACTH y glucagn (3).
cidos grasos esenciales
El organismo tiene una gran habilidad para sintetizar muchos componentes; as, el exceso de
protenas y carbohidratos puede ser convertido en grasa (3). Sin embargo, en 1929, Burr y
Burr (2) sealaron que las ratas alimentadas con una dieta sin grasa y con un aporte
adecuado en el resto de los nutrientes dejaban de crecer, perdan peso y presentaban
problemas en la piel, lesin renal y, eventualmente, llegaban a morir (3). Estas condiciones
pueden ser prevenidas o corregidas si se aade a la dieta cido linoleico (3). De estos
estudios (1,2) surgi el concepto de cido graso esencial: cido graso que es necesario y no
puede ser sintetizado en el cuerpo (3,5). Los cidos grasos se clasifican como esenciales en
funcin de la posicin del primer doble enlace, contando a partir del grupo metilo que est al
final de la cadena de grupos acilos. Los mamferos no poseen enzimas capaces de sintetizar
dobles enlaces en las posiciones n-3 y n-6 del cido graso; por ello, necesitan obtener con la
dieta los cidos grasos esenciales linoleico y alfa-linolnico (4,5). Durante muchos aos,
los cidos grasos poliinsaturados linoleico, linolnico y araquidnico fueron considerados
esenciales; sin embargo, recientes investigaciones han mostrado que el cido araquidnico
puede ser sintetizado en el cuerpo a partir del linoleico y, por tanto, no tiene que ser
necesariamente suministrado como tal en la dieta (3). Las interrelaciones entre estos cidos
grasos se resumen en la tabla 2.
Funciones estructurales
El almacenamiento excesivo de grasa no slo parece antiesttico e indeseable, sino que se
relaciona con diversos perjuicios para la salud; pero una cierta cantidad de grasa corporal es
necesaria, ya que protege los rganos y el cuerpo de lesiones y golpes y lo asla frente a los
cambios de temperatura, tanto por elevacin como por descenso trmico3. Por otra parte,
los lpidos, en particular los fosfolpidos, ejercen un importante papel en la integridad
estructural y en la funcin de las membranas de las clulas; adems, al ser hidrosolubles
ayudan en el transporte de otras grasas dentro y fuera de las clulas (3).
Funciones reguladoras
En combinacin con otros nutrientes, las grasas proporcionan una textura que aumenta la
palatabilidad de los alimentos, haciendo ms apetecible su consumo. Tambin retrasan el
vaciado del estmago, contribuyendo a la sensacin de saciedad. El colesterol es un
componente incluido en el grupo de las grasasque, aunque tiene una srdida historia y se
suele asociar solamente con aspectos negativos, es el antecesor qumico de diferentes
hormonas, como las de las glndulas adrenales, ovarios y testculos (hormonas esteroideas) y
de las sales biliares (3,6,10).
Los cidos grasos poliinsaturados (AGP) ayudan a construir los fosfolpidos de las
membranas; pero, adems, forman parte de una serie de reguladores metablicos, llamados
eicosanoides, que funcionan en los sistemas cardiovascular, pulmonar, inmune, secretor y
reproductor (5,6,10). En concreto, a partir del cido linoleico puede obtenerse el cido
araquidnico, que es el precursor de productos con elevada actividad biolgica:
prostaglandinas, tromboxanos y prostaciclinas (5,9,10).
Finalmente, las grasas de la dieta sirven como transportadores de vitaminas liposolubles (A,
D, E y K) y ayudan a su absorcin en el intestino (3).
RECOMENDACIONES DIETTICAS Y SITUACIN ACTUAL
Los resultados de los ltimos estudios han llevado a establecer unos objetivos nutricionales
sobre el consumo de grasa (tabla 3) encaminados a mantener la salud y disminuir el riesgo
de aparicin y progreso de diversas patologas (11-14).
Tabla 3. Objetivos nutricionales sobre consumo de grasa establecido para la poblacin
espaola en comparacin con la situacin actual (11-14)

Algunas pautas aconsejan incluir en la dieta 2 g/da de cido linolnico + 200 mg de cido
docosahexaenoico (13).
Recomendaciones dietticas de cidos grasos esenciales
La investigacin ms reciente en torno a los cidos grasos esenciales se ha centrado en la
importancia de la relacin entre el cido linoleico respecto al linolnico y si esta relacin
influye en el desarrollo de algunas enfermedades (5,8,15).
Se piensa que la dieta del paleoltico era ms rica en fuentes marinas y vegetales de cidos
grasosomega-3 y ms baja en omega-6, por lo que la relacin omega-6/omega-3 era de 1:1.
Sin embargo, en la actualidad el consumo de cidos omega-6 ha aumentado y la
relacin omega-6/ omega-3 es de 8-12:1(4,9). En este sentido, las recomendaciones de la
OMS sugieren que la relacin debe ser ms baja: de 5-10:1, aproximadamente (4,16). Otros
autores aconsejan que la relacin entre cido linoleico y linolnico sea de 2-5:1 (8,17).
Parece que no hay ventajas aparentes en tomar ms del 6% de la energa a partir del cido
linoleico. Adems, un consumo elevado tiene el inconveniente de inhibir la sntesis de DHA y
EPA a partir del cido alfa-linolnico (9).
La estimacin de los requerimientos mnimos de cidos grasos esenciales se basa con
frecuencia en elReport of the Panel on Dietary Reference Values of the Committee on Medical
Aspects of Food Policy (18), que sugiere que los requerimientos mnimos de cido linoleico
sean el 1% de la ingestin energtica diaria y los de alfa-linolnico, del 0,2%. The British
Nutrition Foundation Task Force on Unsaturated Fatty Acids (19) recomienda un consumo
equivalente a 1-2 porciones de aceite de pescado por semana o la ingestin diaria de 0,5-1,0
g de cidos grasos omega-3 de cadena larga. Otros organismos aconsejan que el linoleico y
el linolnico aporten el 3-5 y 0,5-1% de la ingestin energtica, respectivamente (5).
FUENTES ALIMENTARIAS DE LOS DIFERENTES TIPOS DE CIDOS GRASOS
Los cidos grasos saturados derivan tanto de grasas animales como vegetales, aunque la
procedencia fundamental de la grasa saturada en la dieta actual deriva de la carne y, en
menor medida, de los productos lcteos.
En los aceites vegetales, segn su tipologa, predomina un cido graso saturado u otro. As,
por ejemplo, el aceite de palma es rico en cido palmtico, la manteca de cacao tiene sobre
todo cido esterico y en el aceite de coco predomina el cido lurico. Por otra parte,
la grasa de la mantequilla es rica en varios cidos grasos saturados: palmtico, oleico y
esterico, y el sebo de vaca tiene cantidades similares de cido palmtico y esterico (10)
(tabla 4).
Tabla 4. Contenido en cidos grasos de algunos aceites vegetales (% de cidos grasos) (20)

El cido oleico, cido graso monoinsaturado, puede ser sintetizado tanto por animales como
por vegetales y se encuentra en elevada proporcin en los aceites de oliva y de colza (10)
(tabla 4).
Otros aceites vegetales tienen sobre todo cidos grasos poliinsaturados; en casi todos
predomina el aporte de cido linoleico (aceites de soja, girasol, maz y germen de trigo),
aunque el aceite de linaza es ms rico en cido linolnico. Los aceites de pescado tambin
son muy poliinsaturados y tienen un elevado contenido encidos grasos omega-3 de cadena
muy larga (10).
La mayor proporcin de cido linolnico es de la forma alfa y se encuentra en los aceites de
soja, colza y, en menor concentracin, en vegetales verdes, almendras y avellanas (15,21)
(tabla 4).
IMPORTANCIA DE LA GRASA EN LA SALUD
La influencia de la cantidad y el tipo de grasa consumida en la elevacin del colesterol
sanguneo y en el aumento del riesgo cardiovascular ha sido tema central de atencin
durante los ltimos aos. Por otra parte, esta implicacin posiblemente haya sido la que ms
trascendencia ha tenido entre los profesionales sanitarios y la poblacin general, al pensar en
la relacin nutricin-salud (22). Es cierto que un excesivo consumo de grasa saturada (y en
menor medida de colesterol) puede provocar elevaciones en el colesterolsanguneo,
especialmente en personas predispuestas, y a largo plazo aumentar el riesgo cardiovascular.
Sin embargo, recientemente se han realizado interesantes estudios que han puesto de
relieve la importancia de diversas fracciones de la grasa en la proteccin cardiovascular y en
el riesgo/proteccin frente a otras muchas patologas como hipertensin, diabetes, procesos
inflamatorios, enfermedades pulmonares, problemas de visin, desarrollo del neonato (5)...
Enfermedades cardiovasculares
Las enfermedades cardiovasculares son la mayor causa de mortalidad en pases
industrializados y uno de los ms importantes problemas de salud pblica. Por supuesto, el
control del colesterol y fracciones lipdicas sanguneas es muy importante en la reduccin del
riesgo cardiovascular (7). En este sentido, el consumo degrasa saturada, colesterol y cidos
grasos trans se asocia positivamente con el riesgo de padecer una enfermedad
cardiovascular, mientras que los cidos grasos cis, mono y poliinsaturados parecen
relacionarse de manera inversa con el riesgo de sufrir este tipo de procesos (23,24) (figura
3).

Fig. 3
Estudios realizados en humanos ponen de relieve la existencia de una relacin inversa entre
ingestin de cido linoleico o alfa-linolnico y mortalidad cardiovascular. Por otra parte, el
efecto combinado (asociado al consumo de los dos cidos grasos) resulta sinrgico en la
proteccin frente a este tipo de patologas (9,25).
El mecanismo por el cual el alfa-linolnico modifica el riesgo coronario en humanos no es
bien conocido; tambin se desconoce el efecto de modificar la relacin linoleico/linolnico y
de AGP/AGS (9). El efecto beneficioso puede estar mediado porque el cido alfalinolnico

puede ser utilizado en la sntesis de cidos grasos poliinsaturados de cadena larga, con
efectos cardioprotectores. Concretamente, despus de su ingestin, el cido alfa-linolnico se
convierte rpidamente en EPA y ms lentamente en DHA (26), los cuales disminuyen las
arritmias cardiacas (15,27,28); el EPA puede proteger tambin frente a la trombosis (29).
Los esteroles vegetales y sus formas hidrogenadas (estanoles) provocan descensos
del colesterolsanguneo y, como consecuencia, suponen una proteccin frente a las
enfermedades cardiovasculares (30,31). El mecanismo exacto por el que los esteroles
vegetales disminuyen el colesterol no es totalmente conocido, pero parece que compiten con
l por su similitud estructural (figura 2) en el intestino, impidiendo su solubilizacin por
accin de las sales biliares. Al no poder ser solubilizado, parte del colesterol (el exgeno,
procedente de los alimentos, y el producido endgenamente en el cuerpo) no puede ser
absorbido y es excretado con las heces (30,31).
Los resultados de estos estudios han llevado a incorporar esteroles vegetales, en su forma
esterificada, en una margarina como alternativa en la lucha contra la elevacin
del colesterol sanguneo. En este sentido, un estudio clnico realizado en 1999 demostr que
el consumo de diferentes cantidades de esteroles vegetales(0,85, 1,6 y 3,3 g) contenidos en
una margarina causaban un descenso clnicamente relevante en las concentraciones de
colesterol LDL: 6,7, 8,5 y 9,9%, respectivamente (30).
Hipertensin
Existen estudios de intervencin que sugieren un efecto hipotensor de la grasa
monoinsaturada de la dieta cuando sustituye a la grasa saturada (32). En otros se ha
observado el efecto beneficioso en la reduccin de la presin arterial de la sustitucin
isocalrica de una dieta rica en grasa saturada por grasa insaturada,
tanto monoinsaturada como poliinsaturada (32,33).
Por su parte, Iso y cols. (34) sealan que aumentar la ingestin de cido linoleico puede
proteger frente a accidentes cerebrovasculares por disminuir la presin arterial, la agregacin
plaquetaria y aumentar la deformabilidad de los eritrocitos.
Diabetes
Tanto la cantidad como el tipo de grasa consumido pueden modificar el metabolismo de la
glucosa y la insulina (35). En este sentido, el estudio realizado por Salmern y cols. (36)
seala que la ingestin de cidos grasos trans aumenta y la de cidos grasos
poliinsaturados disminuye el riesgo de padecer diabetes tipo 2. Por otra parte, una dieta rica
en cidos grasos monoinsaturados (19% de la energa) provoca cambios beneficiosos en la
glucemia en ayunas y en la tolerancia a la glucosa. El efecto parece ser debido a cambios en
las proporciones de oleico, alfa-linolnico y araquidnico en los fosfolpidos (35) (figura 3).
Procesos inflamatorios
Los cidos linoleico y linolnico son metabolizados para producir cido araquidnico y EPA,
respectivamente, en el intestino, hgado y cerebro del ser humano (tabla 5). Dada la
abundancia relativa en la dieta de cido linoleico, el compuesto mayoritario incorporado a los
fosfolpidos de las membranas celulares es el araquidnico, con la consiguiente repercusin
en los procesos de agregacin plaquetaria e inflamacin (37). Sin embargo, modificando la
ingestin lipdica se puede desviar el equilibrio de los eicosanoides hacia la formacin de
compuestos con menor actividad inflamatoria (5,38).
Tabla 5. Influencia de la ingestin de cidos grasos en los procesos de agregacin plaquetaria
e inflamacin

Por otra parte, la modificacin del contenido en cidos grasos de la dieta y, en concreto, el
aumento en el consumo de cidos grasos omega-3 (39), cido gammalinolnico (40) y cido
eicosatrienoico (C20:3 n-9) (37) aportan beneficios en la artritis reumatoide, al inhibir la
produccin de ciertos eicosanoides y citocinas implicados en la aparicin de procesos
inflamatorios (37).
Enfermedades pulmonares
Investigadores como D.F. Horrobin han establecido la hiptesis de que la baja prevalencia de
enfermedad pulmonar entre los esquimales es el resultado de las peculiaridades de su dieta,
que contribuye a disminuir la produccin de eicosanoides a partir del cido araquidnico, de
forma que se reduce la produccin de leucotrienos broncoconstrictores. En este mismo
sentido, algunos estudios epidemiolgicos muestran que un aumento en el consumo de
pescado y de cidos grasos omega-3 tiene efectos protectores frente al asma (especialmente
en nios) y ayuda a disminuir el riesgo de de bronquitis y enfisema. Todo esto indica que
loscidos grasos desempean un papel en la disminucin del riesgo de las enfermedades
pulmonares, aunque son necesarios ms estudios al respecto (41).
Muchas de las investigaciones realizadas parecen avalar la conveniencia de aumentar el
consumo de cidos grasos omega-3 para disminuir el riesgo o frenar el progreso de
numerosas enfermedades crnicas, controlando tambin la relacin cido linoleico/cido
linolnico (LA/ALA). Sin embargo, al aumentar el consumo de grasa poliinsaturada pueden
producirse fenmenos de peroxidacin que podran ser negativos desde el punto de vista
sanitario. Se debe analizar si la ingestin de antioxidantes tiene que ser modificada
paralelamente con la de cidos grasos insaturados (5).
Problemas de visin
El aumento en el consumo de grasa se relaciona con una mayor incidencia de degeneracin
macular. El efecto parece deberse a la accin de algunos cidos grasos, ms que a la accin
de la grasa per se. Concretamente, la ingestin de cido linoleico se asocia con un aumento
en el riesgo de degeneracin macular, mientras que el consumo de cido docosahexaenoico
(DHA) muestra una leve relacin inversa y aumentar el consumo de pescado reduce el riesgo
de sufrir esta degeneracin (42).
Tambin las concentraciones sanguneas de DHA estn inversamente relacionadas con el
padecimiento de enfermedades degenerativas de la retina como la retinitis pigmentosa (43).
Desarrollo del neonato y primeras etapas de la vida
Se ha sugerido que la capacidad de sntesis del cido araquidnico (a partir del cido
linoleico) puede estar limitada en neonatos (44,45), por lo que es importante cuidar el aporte
de cidos grasos en las primeras etapas de la vida del individuo.
Varios estudios han demostrado que los nios alimentados con frmulas que incluyen slo LA
y ALA tienen menor capacidad visual que los alimentados con frmulas suplementadas con
DHA y otros cidos grasos poliinsaturados de cadena larga (46,47). Tambin se ha
cuestionado la relacin LA/ALA ms adecuada para las frmulas infantiles, dado que la
cantidad de DHA que el nio puede sintetizar est influida por esta relacin. En concreto, el
estudio de Makrides y cols. (48) pone de relieve que los nios alimentados con frmulas que
tienen una relacin LA/ALA de 5:1 tienen menor cantidad de DHA en fosfolpidos de
eritrocitos y plasma que los que siguen lactancia materna, pero ms que los que toman
frmulas con relacin LA/ALA de 10:1.

En lo que se refiere al embarazo y la lactancia, parece importante vigilar la dieta materna,

por lo que se propone como conveniente que la relacin linoleico/alfa-linolnico sea de 4:1 a
10:1 en gestantes y que la excesiva ingestin de cido linoleico sea evitada (45).
CONCLUSIN
Son necesarios ms estudios sobre los efectos de los diferentes tipos de grasas de la
alimentacin en el organismo, ya que las grasas son un grupo de compuestos heterogneos y
de gran complejidad. Muchos interrogantes tienen que ser despejados todava, pero no cabe
duda de que las grasas son mucho ms que una fuente de energa y un condicionante del
riesgo cardiovascular (5).
Puesto que cambiar los hbitos de vida es difcil y se asocia con riesgos de carencias y
desequilibrios nutricionales, existen nuevas alternativas de enriquecimiento de alimentos con
algunos nutrientes (esteroles vegetales, cidos grasos n-3, etc.) que pueden ayudar a
conseguir beneficios sobre la salud
http://www.institutoflora.com/importancia-de-las-grasas.php

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Cmo afectan la frituras a la salud?

Las grasas o lpidos son nutrientes que contienen los alimentos y que son
empleados por el cuerpo para construir membranas celulares, tejido nervioso y
hormonas. Tambin se utiliza como combustible. Sin embargo, comer
demasiadas frituras es daino para la salud.
Cabe destacar que la grasa que se ingiere y no se quema en forma de energa,
ni se utiliza para construir los elementos bsicos del cuerpo se almacena en
forma de clulas adiposas. As el organismo se anticipa y previene aquellos
momentos en que el alimento podra escasear.
As mismo, un consumo excesivo de grasas en la alimentacin se ha
relacionado con el aumento del riesgo de obesidad, especialmente con
adiposidad abdominal, que es determinante de la resistencia a la insulina y
representa el factor de riesgo ms importante para diabetes tipo 2, sndrome
metablico, riesgo elevado de enfermedad cardiovascular y muerte prematura.
En la balanza
Las grasas:

Aportan caloras y cidos grasos esenciales.

Ayudan a absorber las vitaminas A, D, E y K, y sustancias con actividad

antioxidante como los carotenoides.

Son necesarias para mantener la piel y el cabello saludables, y la

temperatura del cuerpo.

Juegan un papel fundamental en el transporte, mejoramiento, liberacin

del sabor y en el desarrollo de una textura particular que gusta mucho,
cuando los alimentos se fren.

No obstante, las preparaciones fritas deben solo formar parte del men
ocasionalmente debido a que aumentan las grasas en la sangre y, en
consecuencia, nos hace ms propensos a sufrir enfermedades cardiovasculares,
sobrepeso y obesidad. Ademas, las altas temperaturas pueden destruir algunas

de las vitaminas y minerales de los alimentos, y recientes estudios sugieren el

aumento de posibilidades de padecer de cncer de colon y de seno.
Tips

Cada alimento requiere de una ptima temperatura y de un tiempo para

frer, pero bsicamente estar listo cuando adquiera un color marrn
dorado y se vuelva crujiente.

Si se retira antes de tiempo o se introduce en un aceite que no est bien

caliente, la absorcin del aceite aumenta sbitamente y el alimento se
vuelve ms grasoso y menos agradable al gusto.

La cantidad de aceite que se absorbe durante la fritura es variable y va a

depender no solamente del tiempo de coccin y de la temperatura, sino
tambin, de la naturaleza de cada alimento.

No mezcle aceite nuevo con el ya usado.

Filtre siempre el aceite luego de cada fritura para as eliminar los restos
de alimentos quemados que favorecen la descomposicin de los aceites.

Cambie el aceite frecuentemente, no lo reuse ms de dos o tres veces.

Elimine el exceso de aceite del alimento frito con papel absorbente.

Una forma de reducir la absorcin de aceite entre 20 y 50% es usando la

harina de arroz para enharinar los alimentos a frer.

Sabas que...
No se deben usar aceites que al calentarse produzcan humo, que chispeen
excesivamente al incorporar el alimento, que presenten una tonalidad oscura o
huelan rancio porque ese aceite est deteriorado. No slo implica que
modificar el sabor del alimento, sino que se traduce en el consumo de gran
cantidad de radicales libres que daarn las clulas de nuestro cuerpo.
http://www.fundacionbengoa.org/informacion_nutricion/frituras.asp

RESUMEN Accin y destino de los antioxidantes naturales y sintticos

durante el proceso de fritura. La accin de antioxidantes para retrasar la
oxidacin en grasas y aceites es bien conocida aunque la mayor parte de la
informacin est relacionada con su actividad a temperatura ambiente
durante el almacenamiento o a las temperaturas moderadas de los ensayos
de oxidacin acelerada. Sin embargo, su efectividad a la temperatura
elevada de procesos como la fritura es ms compleja debido a la existencia
de reacciones oxidativas y trmicas que tienen lugar simultneamente. En
esta revisin, se resumen los estudios principales que definen la accin de
los antioxidantes naturales y sintticos durante el proceso de fritura. Se ha
dividido en dos partes que resumen la accin y los compuestos de
degradacin de los antioxidantes naturales, es decir, tocoferoles y otros
compuestos fenlicos presentes en aceites de oliva, ssamo y salvado de

arroz, y de los principales antioxidantes sintticos como BHA, BHT y TBHQ.

PALABRAS CLAVE: Antioxidantes sintticos BHA BHT Compuestos
fenlicos Fritura TBHQ Tocoferoles. SUMMARY Action and fate of natural
and synthetic antioxidants during frying. The action of antioxidants to delay
lipid oxidation in fats and oils is well known although most of the information
is related to their effects at room temperature during storage or at the
moderate temperatures of the accelerated tests to measure oil stability.
However, oxidation at the high temperatures of food processes like frying, is
more complex because the availability of air is unknown and both oxidative
and thermal reactions are simultaneously involved. In this review, the main
studies defining the action of natural and synthetic antioxidants at frying
temperatures are summarized. This review has been divided into two main
parts concerning the information on natural antioxidants, i.e. tocopherols
and other phenolic compounds present in specific oils like olive, sesame and
rice bran oils, and on synthetic antioxidants, i.e. BHA, BHT and TBHQ. KEYWORDS: BHA BHT Frying Phenolic compounds Synthetic antioxidants
TBHQ Tocopherols. Action and fate of natural and synthetic antioxidants
during frying By S. Marmesat, A. Morales, J. Velasco and M.C. Dobarganes*
Instituto de la Grasa (CSIC). Avda. Padre Garca Tejero, 4. 41012- Sevilla
(*Corresponding author: cdobar@cica.es) 1. INTRODUCTION The action of
antioxidants to delay lipid oxidation in fats and oils is well known although
most of the information is related to their effects at room temperature
during storage or at the moderate temperatures of accelerated tests. At
room or moderate temperatures, autoxidation reactions taking place
through chain reactions of free radicals are relatively slow; the
hydroperoxides are the major products formed and their concentration
increases until advanced stages of oxidation. Under these conditions, the
activity of primary antioxidants is due to their ability to donate a hydrogen
to the lipid free radicals preventing a new lipid molecule from entering in the
chain to be oxidized. However, oxidation at the high temperatures of food
processes like frying is far more complex because both oxidative and
thermal reactions are simultaneously involved. At high temperatures, the
formation of new compounds is very rapid, the oxygen pressure is reduced,
and the hydroperoxides decompose rapidly and are practically absent above
150C, indicating that the decomposition of hydroperoxides becomes faster
than their formation (Dobarganes, 1998). As a result, dimeric and oligomeric
triglycerides form from the very early stages of heating and a significant
part of the new compounds formed are non-oxygenated compounds due to
the combination of two variables: high temperature and low oxygen
pressure (Dobarganes and Mrquez-Ruiz, 2007). The information on the fate
of antioxidants at frying temperatures is limited. Chemical degradation of
antioxidants seems to be the major pathway for antioxidant loss at high
temperatures although volatilization and steam distillation due to both the
high temperature and the large amount of steam water escaping from the
food have also been postulated. In this review, the main studies on the
action of antioxidants in the frying process and on their degradation
compounds formed are evaluated. This review has been divided into two
main parts concerning the information on natural and synthetic antioxidants
334 grasas y aceites, 61 (4), octubre-diciembre, 333-340, 2010, issn: 00173495, doi: 10.3989/gya.021910 S. Marmesat, A. Morales, J. Velasco and M.C.

Dobarganes 2. NATURAL ANTIOXIDANTS 2.1. Tocopherols and tocotrienols

The protection of tocopherols at the high temperatures of the frying process
has been demonstrated by comparing the formation of new compounds in
natural oils and tocopherol-stripped oils. For oils of different degrees of
unsaturation, the degradation was significantly higher when the tocopherols
were absent although their activity seemed to be more related to the type of
natural tocopherols present in the oil than to the degree of oil unsaturation
(Barrera Arellano et al., 2002). However, at low temperatures and at
temperatures used in oxidative accelerated tests (100-120C), the loss in
tocopherols clearly depended on the degree of unsaturation (Yuki and
Ishikawa 1976; MartinPolvillo et al., 2004; Mrquez-Ruiz et al., 2008). Thus,
a mechanism dependent on temperature seems to be involved in their
action (Marinova and Yanishlieva, 1992). As an example, Figure 1 shows the
different behavior of tocopherols, depending on the temperature, in
conventional high linoleic and genetically modified high oleic sunflower oils,
i.e., oils with similar tocopherol compositions but differing in the composition
of triacylglycerols. Figure 1A shows the formation of polar compounds in the
sunflower oils with and without their natural tocopherols heated at 180C for
10 hours (surface-to-volume ratio was 0.4), as well as the parallel loss of
tocopherols when they were present in the samples (Barrera Arellano et al.,
2002). As it can be observed, similar levels of tocopherols were present in
both oils, with more than 95% being a-tocopherol. The action of the natural
antioxidants is clearly demonstrated by the higher levels of polar
compounds of the stripped oils at any heating period. However, the effect of
tocopherols in delaying the formation of polar compounds was similar
regardless of the degree of oil unsaturation. Figure 1B and Figure 1C show
the formation of polar compounds and the loss in tocopherols in the same
oils at room temperature and at 100C in the conditions of the Rancimat
test (Martn Polvillo et al., 2004; Mrquez- Ruiz et al., 2008). In both cases,
the action of tocopherols was clearly dependent on the degree of
unsaturation. It is important to note that apart from the different
temperature, the availability of air may also have an important contribution
to the results obtained. At frying temperatures there is air limitation, as air
solubility decreases with increasing temperature and no bubbling of air was
applied. However, at room temperature and at 100C there was no
restriction of air. The most important difference concerns the rapid
exhaustion of tocopherols at frying temperatures and particularly in the less
unsaturated oil (Yuki and Ishikawa, 1976; Yoshida et al., 1990; Jorge et al.,
1996a; 1996b; Simone and Eitenmiller, 1998; Wagner et al., 2001; Barrera
Arellano et al., 2002; Mara et al., 2009). Not only was the loss of tocopherols
more rapid in the least unsaturated oil, but also tocopherols were exhausted
at lower oil degradation. These results have been reported in different
studies either in model systems (Barrera Arellano et al., 1999; Verleyen et
al., 2001a) or in oils of different degrees of unsaturation and types of
tocopherols (Jorge et al., 1996a, 1996b; Normand et al., 2001; Barrera
Arellano et al., 2002; Verleyen et al., 2002). From these results it is deduced
that, on one hand, special attention should be paid to frying operations
using monounsaturated oils, as they become unprotected at levels of polar
compounds much lower than the limit established in official regulations for
discarding fats for human consumption (25 wt % Figure 1 Formation of polar

compounds (increasing lines) and loss in natural tocopherols (decreasing

lines) in high linoleic () and high oleic () sunflower oils. A) Oils heated at
180C hollow symbols correspond to tocopherol-stripped oils. B) Oils
heated at 100C under Rancimat conditions. C) Oils stored at room
temperature. 0 100 200 300 400 500 0 10 20 30 40 50 60 Storage period
(days) Polar Compounds (%) 0 100 200 300 400 500 600 Tocopherols
(mg/kg) A B C 0 2 4 6 8 10 0 5 10 15 20 25 30 Heating period (hours) Polar
compounds (%) 0 100 200 300 400 500 600 Tocopherols (mg/kg) 0 5 10 15
20 25 0 10 20 30 40 50 Heating period (hours) Polar Compounds (%) 0 100
200 300 400 500 600 Tocopherols (mg/kg) 0 100 200 300 400 500 0 10 20
30 40 50 60 Storage period (days) Polar Compounds (%) 0 100 200 300 400
500 600 Tocopherols (mg/kg) A B C 0 2 4 6 8 10 0 5 10 15 20 25 30 Heating
period (hours) Polar compounds (%) 0 100 200 300 400 500 600 Tocopherols
(mg/kg) 0 5 10 15 20 25 0 10 20 30 40 50 Heating period (hours) Polar
Compounds (%) 0 100 200 300 400 500 600 Tocopherols (mg/kg) grasas y
aceites, 61 (4), octubre-diciembre, 333-340, 2010, issn: 0017-3495, doi:
10.3989/gya.021910 335 Action and fate of natural and synthetic
antioxidants during frying was formed in great amounts, starting to
decrease after 5-hour heating. The time course of a-tocopherol
thermoxidation shows that a-tocopherolquinone was formed at a lower
concentration. Similar results have been obtained by Verleyen et al. (2001a;
2001b) in model systems of triolein and tripalmitin mixtures. The formation
of a-tocopherolquinone has also been recently reported in sunflower and
soybean oils heated at 180C with and without a-tocopherol added,
.although no quinones from g- and d- tocopherols were identified in soybean
oil (Rennick and Warner, 2006). Surprisingly, with polymerization being the
most specific reaction in frying from the first stages of heating, the
formation of dimeric and polymeric molecules from tocopherols has been
mainly reported at low or moderate temperatures (Kamal-Eldin and
Appleqvist, 1996; Gogolewski et al., 2003). Only Fujitani and Ando (1977)
reported the formation of two dimers of g-tocopherol: 5-(g-tocopheroxy) gtocopherol and 5-(g-tocopherol-5-yl) g-tocopherol) after heating at 180C
saturated and unsaturated triglycerides containing g-tocopherol. Although
the mechanism of tocopherol degradation at high temperatures is not fully
understood, their direct reaction with oxygen has been suggested (Verleyen
et al., 2001b). Also, the low amounts found for oxidation compounds of
tocopherol with respect to their high loss and their evolution as the heating
period increases are indications of the formation of other unknown
degradation compounds and also of the further degradation of the initial
oxidation compounds formed. 2.2. Other natural antioxidants There are
three groups of natural antioxidants whose beneficial action in frying has
been consistently reported. These are polyphenols in virgin olive oils, mainly
comprised by hydroxytyrosol, tyrosol and their derivatives, and lignans
(Bendini et al., 2007; Cicerale et al., 2009); g-oryzanol, i.e. sterol esters of
ferulic acid, in rice bran oil (Lerma-Garcia et al., 2009); and lignans, mainly
sesamine, sesamolin and sesamol, in sesame oil (Moazzami et al., 2007;
Namiki, 2007). The good performance of virgin olive oil in frying as
compared to refined olive oil is mainly attributed to the presence of
polyphenols. Interestingly, studies analyzing the evolution of tocopherols
and polyphenols during frying reported a high rate of degradation for

hydroxytyrosol and its derivatives, a similar or lower rate for a-tocopherol

and a low degradation rate for tyrosol, its derivatives and lignans
(Andrikopoulos et al., 2002; Brenes et al., 2002; Gmez-Alonso et al., 2003;
Nissiotis and Tasioula-Margari, 2003; Carrasco-Pancorbo et al., 2007;
Daskalaki et al., 2009). Therefore, the effective protection found is probably
more related to the group of less active antioxidants present, i.e., lignans
and tyrosol and their derivatives, which remain longer at frying
temperatures. There have been a limited number of reports on the good
frying performance of pure sesame and polar compounds). If the fried food
has to be stored, oxidation at low temperature would be very rapid in the
absence of antioxidants regardless of the degree of unsaturation (Marquez
Ruiz et al., 1999). On the other hand, these results indicate that accelerated
tests at moderate temperatures or under the conditions of Rancimat tests
may be useful to predict the relative shelf-life of different oils and fats but
they would not give an indication of their frying performance. Concerning
the type of tocopherols, the relative stability of -, -, - and -tocopherol at
high temperatures has been studied in detail and there is agreement that tocopherol is less stable than -tocopherol, while - and -tocopherols would
degrade at intermediate rates (Yoshida et al., 1991a, 1991b, 1992, 1993;
Gordon and Kourimska, 1995a; Lampi and Kamal Eldin, 1998; Barrera
Arellano et al., 1999, 2002). In this respect, new sunflower lines that contain
g-tocopherol as the major natural antioxidant instead of a-tocopherol, which
is characteristic of standard sunflower oil, are of special interest (Demurin et
al., 1996; Velasco et al., 2004; Marmesat et al., 2008). The higher protection
given by g-tocopherol as compared to a-tocopherol regardless of the oil
used (Lampi and Kamal Eldin, 1998; Barrera Arellano et al., 2002) and the
present possibilities of new oils of low degree of unsaturation allow for a
foreseeable future when processor needs and consumer demands will be
met (Marmesat et al., 2008). The action of tocotrienols has been less
studied. In general, the stability of a-tocotrienol was found to be similar to
that of a-tocopherol both in palm olein and in purified oils containing both
antioxidants added (Simone and Eitenmiller, 1998; Wagner et al., 2001;
Romero et al., 2004, 2007; Schroeder et al., 2006; Rossi et al., 2007).
However, the order of stability of the different tocotrienol homologues was
different to that found for their tocopherol counterparts, being g-tocotrienol
the least stable (Simone and Eitenmiller, 1998; Rossi et al., 2007). The
information on the fate of tocopherols at elevated temperatures is limited,
which contrasts with the works on the chemistry of oxidation at room
temperature or under the conditions of accelerated test without air
limitation. In an excellent review by Kamal-Eldin and Appleqvist (1996) the
most significant information on changes at room or moderate temperature
can be found in detail. The formation of new compounds at high
temperatures has been studied in model systems (Fujitano and Ando, 1977;
Verleyen et al., 2001a 2001b) and in refined oils (Buchowski et al., 1995;
Murkovic et al., 1997; Rennick and Warner, 2006). It has been reported that
tocopherols have a very low volatility at frying temperature (Pongracz,
1988) and hence, their rapid loss is due to their degradation. Studies on the
oxidation products from a-tocopherol at 90, 180 and 220C report the
formation of a-tocopherolquinone 2,3-epoxide, a-tocopherolquinone 5,6epoxide and a-tocopherolquinone as the major compounds (Murkovic et al.,

1997). However, at high temperatures (180 and 220C) tocopherols

disappear very rapidly (8 hours) and from the two epoxides only the 5,6epoxide 336 grasas y aceites, 61 (4), octubre-diciembre, 333-340, 2010,
issn: 0017-3495, doi: 10.3989/gya.021910 S. Marmesat, A. Morales, J.
Velasco and M.C. Dobarganes used to increase the consumption of natural,
healthy compounds in response to consumer demand and, on the other, to
delay the oil deterioration by protecting the natural antioxidants. Extracts of
rosemary (Gordon and Kourimska, 1995 a, 1995b; Jaswir and Man 1999; Man
and Tan, 1999; Lalas and Dourtoglou, 2003; Kalantzakis and Blekas 2006;
Armalo and Jorge, 2008), tea (Naz et al., 2004), sage (Jaswir and Man, 1999;
Man and Tan, 1999;), oregano (Houhoula et al., 2003,2004), lavender and
thyme (Bensmira et al., 2007), summer savory (Kalantzakis and Blekas,
2006), carob fruit (Bodega et al., 2009), barley seeds (Anwar et al., 2010),
Curcuma (Nor et al., 2008a) and others (Shyamala et al., 2005; Nor et al.,
2008b) are some examples of the high number of reports on the subject. In
general, the action found is positive because the extracts contain potent
antioxidants, which are detailed in an excellent review on the most
important herbs and spices (Yanishlieva et al., 2006). However, the
effectiveness was similar to that found for synthetic antioxidants, such as
BHA and BHT, of low activity (Man and Tan, 1999). In fact, the protective
effect during frying is highly variable even for the same extract because of
the inherent characteristics of natural products, together with the
complexity of the frying process. On one hand, the composition of an
extract, normally poorly defined, may be quite different depending on the
plant variety, extraction method, solvent used for extraction, concentration
added, etc. On the other hand, the antioxidative effect depends on the
frying conditions, on the degree of unsaturation of the oil and on the content
and chemical structure of other oil minor compounds present exerting a
prooxidant or antioxidative action. 3. SYNTHETIC ANTIOXIDANTS The effect
of a wide variety of specific compounds in frying has been studied. Among
them ascorbyl palmitate and synthetic antioxidants, particularly butylated
hydroxytoluene (BHT), butylated hydroxyanisol (BHA), tertiary butyl
hydroquinone (TBHQ) and propyl gallate (PG), stand out. The advantage of
these studies as compared to those undergone on plant extracts is that the
experiments are carried out with individual compounds or combinations of
them and thus, the action obtained is directly related to the compound
studied. Ascorbyl palmitate (AP) has been the subject of detailed
investigations. In some studies, no significant effect was found with respect
to the oil without additives at frying temperature (Augustin et al., 1987;
Ibrahim et al., 1991). In other reports, the addition of AP retarded the
formation of degradation compounds (Andres, 1984; Gwo et al., 1985;
Gordon and Kourimska, 1995b; Satyanarayana et al., 2000; Onal and Ergin,
2002), and increased the stability of tocopherols (Gordon and Kourimska,
1995a), although it was ineffective in protecting fried foods during storage
(Masson et al., 2002). rice bran oil in spite of their wide consumption in
populous Asian countries (Valsalan et al, 2004; Krishna et al., 2005). A
significant number of recent studies, however, report a significant increase
in oil thermostability, as well as a higher retention of natural tocopherols, in
the blends of different oils with either sesame or rice bran oil (Chung et al.,
2004, 2006; Leonardi 2005; Sharma et al., 2006 Shing et al., 2007: Khan et

al., 2008; Farhoosh and Kenary 2009). Because of the positive effect of
lignan compounds and g-oryzanol on oil performance, the addition of
extracts obtained from sesame and rice bran oils or their by-products to oils
of different degrees of unsaturation has been proposed and some
ingredients and special oils have been commercialized (Kochhar, 2000;
2001; Gertz, 2004). The addition of these natural products to oils continues
to be the subject of many studies, not only focused on the increase in oil
thermostability, but also on the retention of compounds of proven health
benefits whose intake would increase by means of fried food consumption
(Nasirullah and Rangaswamy, 2005; Farag et al., 2007; Hemalatha and
Ghafoorunissa, 2007; Lee et al., 2008; Chiou et al., 2009). Information on
the degradation and changes of these groups of compounds of low volatility
is very scarce. There are several recent studies on the oxidation products
formed from phenolic compounds present in virgin olive oil subjected to
oxidation at room or moderate temperatures (Rovellini and Cortesi, 2002;
Antolovich et al., 2004; Ros et al., 2005; Armaforte et al., 2007; Daskalaki et
al., 2009). Mass spectra of oxidized compounds from dialdehydic and
aldehydic forms of oleuropein and ligstroside aglycons have been reported,
although no information on the exact structures an/or their amounts were
given. Nevertheless, new compounds formed at frying temperatures from
the pool of polyphenols have not been reported until now. Native sesame oil
contains predominantly sesamin and sesamolin and a small amount of
sesamol. Neither sesamolin nor sesamin has been found to possess any
appreciable antioxidant activity (Budowski, 1964). However, sesamolin may
be hydrolyzed during frying, due to the food moisture, giving sesamol and
sesaminol (Fukuda et al., 1986; Kochhar, 2001). Both compounds are highly
stable and have a synergistic effect with tocopherols, decreasing oil
degradation (Yoshida and Takagi, 1999). As for rice bran oil phenolic
compounds, information on the expected hydrolysis of g-ozyzanol during
frying has not been found. On the contrary, it has been reported that the
content of oryzanol did not change in practice under usual home frying
conditions, regardless of its initial content in the oil (Krishna et al., 2005).
2.3. Natural plant extracts as oil additives In the last decade a significant
number of studies focused on the positive effects of the addition of plant
extracts, mainly herbs and spices with a double objective. On one hand,
plant extracts are grasas y aceites, 61 (4), octubre-diciembre, 333-340,
2010, issn: 0017-3495, doi: 10.3989/gya.021910 337 Action and fate of
natural and synthetic antioxidants during frying of them with residual
antioxidant activity (Kurechi et al., 1983: Kim and Pratt, 1990). Reaction
mechanisms explaining the main compounds found from BHA, BHT and
TBHQ have been proposed (Hammama and Nawar 1991). Also, dozens of
reaction products from BHA, BHT and TBHQ were detected by HPLC on
normal phase although the structure of the compounds was not identified
(Warner et al., 1986). Finally, regarding the remaining antioxidant activity of
the degradation products from synthetic antioxidants, the low effectiveness
of BHT and BHA under frying conditions suggests that their oxidation
products has no antioxidant activity even if some of them have been
reported as potent antioxidants at room or moderate temperatures (Kurechi
and Kato, 1980). However, from TBHQ, TBBQ was detected as a major
degradation compound at frying temperature (Kurechi et al., 1983: Kim and

Pratt, 1990; Hammama and Nawar 1991) and interestingly, TBHQ was found
to be a major degradation product of heated TBBQ. Thus, the rapid
degradation of TBHQ would be compatible with an important carrythrough
effect attributed to the TBHQTBBQ cycling system (Kim and Pratt, 1990). In
this respect, novel antioxidants derived from TBHQ but with higher oil
solubility, i.e., lauryl TBHQ and lauryl TBBQ, have been found to exert
stronger antioxidant activity than TBHQ at temperatures higher than 140C
(Zhang et al., 2004). 4. FINAL REMARKS Given the complexity of the frying
process and the dependence of the antioxidative effect on the degree of
unsaturation of the oil and on the content and chemical structure of other oil
minor compounds, attention should be paid to the following points: 1. The
action of antioxidants at frying temperature cannot be deduced from their
behavior at low or moderate temperatures. 2. There is a rapid loss in
antioxidants in oils with high contents of monounsaturated fatty acids and
their exhaustion may take place at degradation levels lower than those
recommended for discarding the used frying oils. Thus, special attention for
maintaining a minimum level of antioxidants in fried products to be stored is
necessary. 3. Before the addition of synthetic antioxidants, a rapid test of
thermal treatment is recommended to evaluate the performance of the
specific type of oil to be used under similar frying conditions.
ACKNOWLEDGMENT This work was supported by MICINN (projects AGL
2007-62922 and AGL 2007-63647) and Junta de Andaluca. Synthetic
antioxidants are added to fats and oils to effectively extend their shelf life.
However, as it occurs with natural tocopherols, the loss in antioxidants
under frying conditions was very rapid and their activity was low. In this
case, their low effectiveness was attributed not only to their rapid
decomposition but also to their volatilization at frying temperature. Thus,
when selecting an antioxidant for its use in frying, attention has to be
focused on the amount of active antioxidant remaining after frying and
protecting the fried foods during storage. This amount will depend on the
type of antioxidant and on the level of antioxidant in the frying medium at
the time of each frying operation (Augustin and Berry, 1984). Studies on the
fate of synthetic antioxidants have been carried out by controlling the
volatiles released from the oil during heating as well as the remaining
antioxidants in the oil maintaining their initial structure (Lin et al., 1991;
Warner et al., 1986; Dobarganes et al., 1986; Hammama and Nawar, 1991).
Thus, the amount of decomposed antioxidant can be calculated by
difference (Dobarganes et al., 1986; Hammama and Nawar, 1991). Also,
interesting studies have used radioactively labeled antioxidants to obtain
appropriate material balances (Lin et al., 1981; Warner et al., 1986). From
these studies it is deduced that BHT and TBHQ had the highest volatility,
while BHA had intermediate volatility, and propyl galate was the less volatile
at frying temperature. With regard to their comparative stability against
thermal oxidation the order found was BHT > PG > BHA > TBHQ (Hammama
and Nawar, 1991). However, concerning their effectiveness in decreasing
the formation of new compounds during frying, TBHQ has been reported to
be much more effective than BHA and BHT (Augustin and Berry, 1984;
Gordon and Kourimska, 1995b; Allam and Mohamed, 2002). The most
systematic study has been carried out by Allam and Mohamed (2002) with
the aim of clarifying the effect of the most important synthetic antioxidants

BHT, BHA, PG and TBHQ and their binary and tertiary mixtures with
synergists and tocopherols. The authors evaluated the loss of the oil stability
index of each system in sunflower oil after heating at 180C for one hour. It
was observed that the protection at frying temperature was not related to
the protection given by the antioxidants at low temperature and it was also
concluded that the interaction between antioxidants at high temperature
could lead to a negative or positive synergism. The decomposition products
from BHA, BHT, TBHQ and PG at high temperatures have been studied in
detail by Hammama and Nawar (1991). BHT and PG gave rise to very few
decomposition products as compared to BHA and TBHQ. The compounds
tentatively identified from BHA and BHT were mainly dimeric compounds.
From TBHQ, tertiary butyl benzoquinone (TBBQ) was detected as the major
degradation product along with many dimerized compounds with ether
linkages, some 338 grasas y aceites, 61 (4), octubre-diciembre, 333-340,
2010, issn: 0017-3495, doi: 10.3989/gya.021910 S. Marmesat, A. Morales, J.
Velasco and M.C. Dobarganes Budowski P. 1964. Recent research on
sesamin, sesamolin and related compounds. J. Am. Oil Chem. Soc. 41, 280
285. Carrasco-Pancorbo A, Cerretani L,Bendini A, SeguraCarretero A, Lecker
G, Fernndez-Gutirrez A. 2007. Evaluation of the influence of thermal
oxidation and on the antioxidant activity of extravirgin olive oils, J. Agric.
Food Chem. 55, 4471-4780. Chiou A, Kalogeropoulos N, Salta FN, Efstathiou
P, Andrikopoulos NK. 2009. Pan-frying of French fries in three different edible
oils enriched with olive leaf extract: Oxidative stability and fate of
microconstituents. LWTFood Sci. Technol. 42, 1090-1097. Chung J, Lee Y,
Choe E. 2004. Effects of sesame oil addition to soybean oil during frying on
the lipid oxidative stability and antioxidants contents of the fried products
during storage in the dark. J. Food Sci. 769, C574-C578. Chung J, Lee Y. Choe
E. 2006. Oxidative stability of soybean and sesame oil mixtures during
frying of flour dough. J. Food Sci. 71, C222-C226. Cicerale S, Conlan XA,
Sinclair AJ, Keast RSJ. 2009. Chemistry and health of olive oil phenolics. Crit.
Rev. Food Sci. Nutr. 49, 218-236. Daskalaki D, Kefi G, Kotsiou K, TasioulaMargari M. 2009. Evaluation of phenolic compound degradation in virgin
olive oil during storage and heating. J. Food Nutr. Res. 48, 31-41. Demurin Y,
kori D, Karlovic D. 1996. Genetic variability of tocopherol composition in
sunflower seeds as a basis of breeding for improved oil quality. Plant Breed.
115, 33-36. Dobarganes MC, Mrquez Ruz G. 2007. Formation and analysis
of oxidized monomeric, dimeric and higher oligomeric triglycerides, in
Erickson MD (Ed.), Deep Frying: Chemistry Nutrition and Practical
Applications. 2nd edition, Champaign, Illinois, AOCS, 87-110. Dobarganes
MC, Prez-Camino MC, Gutierrez Rosales F. 1986. Accin protectora de los
antioxidantes BHT y BHA en grasas calentadas a elevada temperatura.
Grasas y Aceites 37, 262-266. Dobarganes MC. 1998. Formation and
analysis of high molecular-weight compounds in frying fats and oil. OCL, 5,
41-47. Farag RS, Mahmoud EA, Basuni AM. 2007. Use crude olive leaf juice
as a natural antioxidant for the stability of sunflower oil during heating. Int.
J. Food Sci. Technol. 42, 107-115. Farhoosh R, Kenary RE. 2009. Antirancidity effects of sesame and rice bran oils on canola oil during deep
frying. J. Am. Oil Chem. Soc. 86, 539-544. Fujitani T, Ando H. 1977. Oxidative
dimerization of tocopherols during the course of thermal oxidation of
saturated and unsaturated triglycerides. J. Japan Oil Chem. Soc. 26, 768-

773. Fukuda Y, Isobe M, Nagata M, Osawa T, Namiki M. 1986. Acidic

transformation of sesamolin, the sesame oil constituent, into an antioxidant
bisepoxilignan, sesaminol. Heterocycles 24, 923-926. Gertz C. 2004.
Optimising the baking and frying process using oil-improving agents. Eur. J.
Lipid Sci. Technol. 106, 736-745. Gogolewski M, Nogala-Kalucka M, Galuba G.
2003. Studies on dimerisation of tocopherols under the influence of methyl
linoleate peroxides. Nahrung/Food 47, 74-78 Gomez-Alonso S, Fregapane G,
Salvador MD, Gordon MH. 2003. Changes in phenolic composition and
antioxidant activity of virgin olive oil during frying. J. Agr. Food Chem. 51,
667-672. REFERENCES Allam SSM, Mohamed HMA. 2002. Thermal stability
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Food Lipids

Action and fate of natural and synthetic antioxidants during frying By S.

Marmesat, A. Morales, J. Velasco and M.C. Dobarganes* Instituto de la Grasa
(CSIC). Avda. Padre Garca Tejero, 4. 41012- Sevilla (*Corresponding author:
cdobar@cica.es)grasas y aceites, 61 (4), octubre-diciembre, 333-340, 2010,
issn: 0017-3495 doi: 10.3989/gya.021910

grasas y aceites, 63 (3), julio-septiembre, 284-289, 2012, issn: 0017-3495

doi: 10.3989/gya.034412 284 Apparent and quantitative loss of fatty acids
and triacylglycerols at frying temperatures By O. Berdeaux1 , S.
Marmesat2 , J. Velasco2 and M.C. Dobarganes2, * 1 Plate-forme ChemoSens,
Centre des Sciences du Got et de lAlimentation, UMR6265 CNRS,
UMR1324 INRA, Universit de Bourgogne, Agrosup Dijon, 21000 Dijon,
France 2 Instituto de la Grasa (CSIC). Avda. Padre Garca Tejero, 4. 41012Sevilla-Spain *Corresponding author: cdobar@cica.es 1. INTRODUCTION A
large number of papers dealing with comparative performance of different
oils and fats at frying temperatures are published every year. Changes in
fatty acid or triacylglycerol composition are analytical data usually
presented, although their discussion is sometimes inadequate and
misleading. The deficient interpretation is due to the form of expression of
results, being the normalized composition one of the most used. This gives
information on the percentages of each FAME or TAG on the whole analyzed.
In fresh refined fats and oils, the normalized composition for FAME and TAG
coincides in practice with the quantitative composition, as their contents are
close to the total oil sample. However, when oils and fats are heated at
frying temperatures a significant percentage of the fatty acyl groups of the
TAG may alter to form oxidized TAG, dimeric and oligomeric TAG. As a result,
the relative FAME composition given is that of the non-altered FAME fraction,
which is the only one eluted in the GC analysis (Dobarganes and Prez
Camino, 1988; Dobarganes and Mrquez-Ruiz, 2007). The objective of this
paper was to evaluate the loss of fatty acids and TAG at frying temperatures
as well as describe the differences between apparent and quantitative loss
of FAME and TAG based on the amounts of polar fatty acids and polar
compounds. 2. EXPERIMENTAL PART 2.1. Samples Olive oil and conventional
sunflower oil were purchased from local outlets and thermoxidized at 180C
as described below. 2.2. Heating procedure Thermal oxidation was carried

out under strictly controlled conditions using a Rancimat (Metrohm,

RESUMEN Prdida aparente y cuantitativa de cidos grasos y especies de
triglicridos a temperatura de fritura. Aceites de oliva y girasol se calentaron
a 180C durante 5, 10 y 15 horas con el objetivo de definir los cambios en la
concentracin de cidos grasos y especies de triglicridos en condiciones de
fritura. Se definen las diferencias entre la prdida aparente y cuantitativa de
cidos grasos y triglicridos que dependen de la forma de expresin de los
resultados dando lugar en muchas ocasiones a interpretaciones err- neas.
As, a partir de la composicin normalizada, podra deducirse que slo el
cido graso ms insaturado en los aceites (C18:2) se altera. Sin embargo,
los datos cuantitativos muestran claramente que en muestras con niveles
de compuestos polares entre 14.6 y 35.4%, todos los cidos grasos
insaturados sufren degradacin significativa en ambos aceites. Con respecto
a los cambios en los distintos triglicridos, su prdida cuantitativa dependi
no slo de su nmero de dobles enlaces sino tambin del contenido del
cido ms insaturado en ambos aceites. PALABRAS CLAVE: cidos grasos
Compuestos polares steres metlicos de cidos grasos polares Fritura
Triglicridos. SUMMARY Apparent and quantitative loss of fatty acids and
triacylglycerols at frying temperatures. Olive and sunflower oils were heated
at 180C for 5, 10 and 15 hours with the aim of defining the changes in the
contents of fatty acid methyl esters (FAME) and triacylglycerols (TAG) under
frying conditions. Differences between apparent and real loss of FAME or
TAG are defined for an adequate interpretation of the changes taking place
at high temperature. Such differences depend on the expression of the
results and frequently result in erroneous conclusions. Results showed that
from the normalized composition it could be deduced that only the most
unsaturated FAME (C18:2) or TAG containing it was significantly altered.
However, quantitative data indicated that all the unsaturated FAME were
degraded in samples of olive oil and sunflower oil whose levels of alteration
ranged from 14.6 to 35.4% polar compounds. With regard to TAG, their loss
depended on both the number of double bonds and the concentration of the
linoleyl group, which is the most unsaturated fatty acyl group in both oils.
KEY-WORDS: Fatty acids Frying Polar compounds Polar FAME
Triacylglycerols. grasas y aceites, 63 (3), julio-septiembre, 284-289, 2012,
issn: 0017-3495, doi: 10.3989/gya.034412 285 Apparent and quantitative
loss of fatty acids and triacylglycerols at frying temperatures Herisau,
Switzerland) apparatus. Samples of olive and sunflower oils were treated
under identical conditions. Samples of 8 0.01 g oil were weighed out in
Rancimat reaction vessels and these were inserted into the heating block of
the Rancimat heated at 180 1C. Samples were heated in triplicates for 5,
10 and 15 h. Rancimat instructions were carefully observed for temperature
correction. No bubbling of air was applied during heating and the tubes were
left open. This procedure was described in detail, including reproducibility
data, in a previous publication (Barrera Arellano et al., 1997). 2.3. Analytical
determinations 2.3.1. Quantitation of polar compounds The content of total
polar compounds was determined gravimetrically following the method
proposed by the IUPAC (IUPAC, 1992c) with slight modifications. Thus, the
non-polar and polar fractions were separated from 1 g of oil by silica column
chromatography. The non-polar fraction, which contains the nonpolar TAG,
was eluted with 150 mL of n-hexane/diethyl ether (90:10, v/v). A second

fraction, which comprises the total polar compounds, was eluted with 150
mL of diethyl ether. After evaporation of solvents, the contents of the
nonpolar and polar fractions were determined gravimetrically. Efficiency of
the separation was checked out by thin layer chromatography using
hexane/diethyl ether/acetic acid (80:20:1, v/v/v) for development of plates
and exposure to iodine vapor to reveal the spots. 2.3.2. Quantitation of
nonpolar and polar fatty acid methyl esters (FAME) FAME were prepared
from 300 mg of oil by basecatalyzed transmethylation with sodium
methoxide in TBME (Cecchi et al., 1985). After evaporation of TBME under
nitrogen, FAME were dissolved in 2 mL of n-hexane-diethyl ether (95:5 v/v)
and then separated into two fractions of different polarity by silica column
chromatography. A 40-cm length and 1-cm i.d. glass column filled with 6 g of
silica adjusted to a water content of 5% (m/m) was used. The nonpolar
fraction was firstly eluted with 50 mL of n-hexane-diethyl ether (95:5 v/v)
and the polar fraction was obtained using 50 mL of diethyl ether. After
evaporation of solvents, nonpolar and polar fatty acids were determined
gravimetrically. The efficiency of the separation was checked out by TLC
using hexane-diethyl ether-acetic acid (80:20:1 v/v/v) for development of
plates and exposure to iodine vapor to reveal the spots. 2.3.3. Fatty acid
composition Fatty acid composition was determined by GC after
derivatization of the oils to FAME with 2N KOH in methanol, according to the
IUPAC Standard Method (IUPAC, 1992a; 1992b). An Agilent 6890 gas
chromatography system (Palo Alto, CA) equipped with a split/split-less
injector, an Innowax capillary column (30 m length, 0.25 mm i.d., 0.20 m
film thickness) and a flame ionization detector (FID) was used. Hydrogen
was used as carrier gas. The detector and injector temperatures were
250C. The initial oven temperature was 180C and a temperature gradient
from 180 to 220C at 3C min1 was applied. Injections were performed
using a split ratio of 1:50. 2.3.4. Triacylglycerol (TAG) composition TAG
species were determined by GC using an Agilent 6890 chromatograph (Palo
Alto, CA) equipped with a split/split-less injector, a Quadrex Aluminum-Clad
400-65HT capillary column (30 m length, 0.25 mm i.d., 0.1 m film
thickness; Woodbridge, CT) and a FID. Hydrogen was used as carrier gas.
The injector and detector temperatures were 360 and 370C, respectively,
the oven temperature was maintained at 335C, and a head pressure
gradient from 100 to 180 kPa was applied. A linear gas rate of 50 cm s1
and a split ratio of 1:80 were used (Fernndez-Moya et al., 2000). The TAG
species were identified and the data corrected for the relative response of
the FID (Carelli and Cert, 1993). 3. RESULTS AND DISCUSSION Table 1 shows
results for polar compounds and polar fatty acids. The olive oil had a higher
thermostability although no great differences were found between the two
oils in spite of their differences in composition. Under the conditions applied,
the polar compounds were between 14.6 and 35.4%, which are normal
contents in used frying fats and oils (Dobarganes and MrquezRuz, 1998).
After 10-hour heating, both oils showed around 25% polar compounds, limit
established in most of the present regulations to discard frying oils and fats
for human consumption. Polar FAME is a measure of the altered fatty acids
and is considered a good measurement of thermoxidative degradation.
Results showed values that ranged from 5.4 to 17.5%. The ratio between
total polar FAME and polar compounds provides a measurement of the

average of polar fatty acids present in polar TAG. For instance, a ratio of
0.37 indicates that 37% of the fatty acids included in polar compounds are
polar fatty acids, while 63% are consequently nonaltered fatty acids. The
ratio increased with the level of degradation and it was similar for similar
levels of polar compounds (Table 1). Table 2 shows the changes in fatty acid
composition for both oils after different periods of heating. As expected, the
level of the most unsaturated fatty acid (C18:2) decreased with 286 grasas
y aceites, 63 (3), julio-septiembre, 284-289, 2012, issn: 0017-3495, doi:
10.3989/gya.034412 O. Berdeaux, S. Marmesat, J. Velasco and M.C.
Dobarganes heating time and, apparently, C18:2 was the only fatty acid that
was degraded. This fact is remarked in a significant number of papers
suggesting that oleic acid does not change during heating and frying.
Moreover, as it could be apparently deduced from data in Table 2, it has
been often concluded that C18:1 and saturated fatty acids even increase
after heating. However, these changes are misleading because of the way of
expression of FAME data as the percentage of each fatty acid on the total
content of those analyzed or normalized composition, i.e. all the rows add
up to 100. In fact this is the relative FAME composition of the nonaltered
FAME fraction, which is the only fraction eluted in the GC analysis. Due to
their high polarity the altered fatty acids are normally adsorbed in the GC
column and do not elute under the analytical conditions applied. Table 3 lists
data which have been modified considering the content of nonpolar FAME in
the samples to show quantitative changes in FAME expressed on the oil
weight. In the first column of Table 3 the real content of FAME (100 % polar
FAME) has been included and the new data have been calculated to add up
to the nonpolar FAME in each row. Assuming that initially the content of
FAME is close to the sample weight (100%), it can be observed that all the
unsaturated fatty acids decreased meanwhile the saturated fatty acids
remained at their initial levels due to their high stability. In Table 4 apparent
and real losses of the different fatty acids have been calculated for 10-hour
heating, when the percentages of polar compounds were around the limit
for frying oil rejection (25% polar compounds) in both oils. The results
indicate that, as expected, the loss of each unsaturated fatty acid was
higher as its degree of unsaturation increases. Based on the absence of
changes in saturated fatty acids, we proposed an indirect measurement of
the thermoxidative alteration through polar FAME by considering the major
saturated fatty acid unchanged (Dobarganes and Prez-Camino, 1988).
Table 5 shows the FAME composition Table 1 Polar compounds and polar
fatty acids (FAME) in olive and sunflower oils heated at 180C for 5, 10 and
15 hours Oil Heating time (h) Polar compounds (wt% on oil) Polar FAME (wt%
on oil) Polar FAME/Polar compounds Olive 0 4.4 0.14* 5 14.6 0.14
5.4 0.21 0.37 10 22.8 0.02 9.9 0.28 0.43 15 30.8 0.07 15.5
0.28 0.50 Sunflower 0 3.6 0.14 5 17.2 0.35 6.5 0.42 0.38 10 26.6
0.07 12.2 0.07 0.46 15 35.4 0.21 17.5 0.28 0.49 * mean
standard deviation (n 5 3). Table 2 Fatty acid composition (%) in olive and
sunflower oils heated at 180C for 5, 10 and 15 hours Oil Heating time (h)
C16:0 C16:1 C18:0 C18:1 C18:2 Others Olive 0 11.1 0.9 2.6 76.2 7.7 1.5 5
11.6 0.9 2.8 76.5 6.7 1.5 10 12.0 0.9 3.0 76.4 5.8 2.0 15 12.8 0.9 3.0 76.3
5.1 1.9 Sunflower 0 6.2 tr 4.6 27.7 59.8 1.7 5 6.8 tr 4.9 27.7 58.2 2.5 10 6.8
tr 5.1 28.3 58.0 1.8 15 7.4 tr 5.4 29.4 56.5 1.3 tr, traces. grasas y aceites,

63 (3), julio-septiembre, 284-289, 2012, issn: 0017-3495, doi:

10.3989/gya.034412 287 Apparent and quantitative loss of fatty acids and
triacylglycerols at frying temperatures considering constant the percentage
of C16:0. The estimated content of nonpolar FAME included in the last
column was close to that obtained by adsorption chromatography (Table 3).
The conclusions drawn from the FAME composition in Table 5 are the same
as those obtained from quantitative data in Table 3. Tables 6 and 7 show
normalized composition of TAG for the samples of olive and sunflower oil,
respectively. The nonaltered TAG fraction obtained in the determination of
polar compounds was used Table 3 Quantitation of fatty acids (wt% on oil) in
olive and sunflower oils heated at 180C for 5, 10 and 15 hours Oil Heating
time (h) Nonpolar FAME C16:0 C16:1 C18:0 C18:1 C18:2 Others Olive 0 100
11.1 0.9 2.6 76.2 7.7 1.5 5 94.7 11.0 0.9 2.7 72.4 6.3 1.4 10 90.1 10.8 0.8
2.7 68.8 5.2 1.8 15 84.5 10.8 0.8 2.6 64.5 4.3 1.6 Sunflower 0 100 6.2 tr 4.6
27.7 59.8 1.7 5 93.3 6.3 tr 4.6 25.8 54.3 2.3 10 87.9 6.0 tr 4.5 24.8 51.0 1.6
15 82.2 6.1 tr 4.4 24.1 46.4 1.1 tr, traces. Tabla 4 Apparent and quantitative
loss of unsaturated fatty acids (%) in olive and sunflower oils heated at
180C for 10 hours Oil Loss C 16:1 C18:1 C18:2 Olive Apparent 0 0 25.7
Quantitative 11.1 9.7 32.5 Sunflower Apparent 0 3.0 Quantitative 10.5
14.7 Table 5 Estimated quantitation of FAME (wt% on oil) by maintaining
constant the initial content of the major saturated fatty acid Oil Heating time
(h) C16:0 C16:1 C18:0 C18:1 C18:2 Others Estimated nonpolar FAME Olive 0
11.1 0.9 2.6 76.2 7.7 1.5 100.0 5 11.1 0.9 2.7 73.2 6.4 1.4 95.7 10 11.1 0.8
2.8 70.7 5.4 1.9 92.6 15 11.1 0.8 2.6 66.2 4.4 1.6 86.7 Sunflower 0 6.2 tr 4.6
27.7 59.8 1.7 100.0 5 6.2 tr 4.5 25.3 53.1 2.3 91.3 10 6.2 tr 4.7 25.8 52.9
1.6 91.2 15 6.2 tr 4.5 24.6 47.3 1.1 83.8 tr, traces. Table 6 Triacylglycerol
composition (%) in olive oil heated at 180C for 5, 10 and 15 hours Heating
time (h) POP PLP POS POO POL SOO OOO SOL OOL 0 3.5 1.2 1.3 24.3 6.2 5.2
43.4 4.2 9.5 5 3.9 1.1 1.4 25.1 5.8 5.3 43.4 3.9 8.4 10 4.1 1.2 1.4 26.2 5.5
5.6 43.6 3.8 7.2 15 4.3 1.2 1.6 26.7 5.0 5.7 43.5 3.8 6.4 288 grasas y
aceites, 63 (3), julio-septiembre, 284-289, 2012, issn: 0017-3495, doi:
10.3989/gya.034412 O. Berdeaux, S. Marmesat, J. Velasco and M.C.
Dobarganes for the analysis of TAG composition to avoid impurification of
the chromatographic column by the altered compounds which do not elute
under the analytical conditions applied. Only TAG containing C18:2
decreased in both oils giving again the apparent impression that C18:1
remained unaltered. Similarly to that commented for FAME, the normalized
composition can be transformed into quantitative data by considering that,
after heating, the nonpolar TAG are only a part of the sample. In Tables 8
and 9 the percentages of nonpolar TAG deduced from polar compounds
(100-% polar compounds) have been included in the first column to
calculate the real contents of TAG expressed on weight sample. Great
differences were observed between apparent and real losses of TAG species
(Table 10). From quantitative data, it was observed that, for example,
around 25% polar compounds, all the TAG underwent degradation because
all contained unsaturated fatty acids. The only exceptions were those TAG
containing one oleyl group as the only unsaturated fatty acyl in sunflower
oil, probably due to the high concentration of TAG containing the linoleyl
group, which is more susceptible to degradation. As expected, the higher
the degree of unsaturation, the higher the loss of TAG. However, it is also

interesting to observe that for TAG species with the same number of double
bonds, the degradation was more rapid as the content of linoleyl groups
increased. This is the case Table 7 Triacylglycerol composition (%) in
sunflower oil heated at 180C for 5, 10 and 15 hours Heating time (h) POP
PLP POS POO PLS POL PLL SOO OOO SOL OOL SLL OLL LLL 0 0.3 1.1 0.3 2.1
1.4 6.7 10.1 1.3 5.6 3.7 11.3 7.3 26.5 22.3 5 0.3 1.0 0.4 2.4 1.4 7.0 10.0 1.5
6.5 3.9 12.1 6.9 26.0 20.6 10 0.4 1.2 0.5 2.6 1.5 7.3 9.8 1.7 6.8 4.2 12.3 7.1
25.1 19.0 15 0.4 1.2 0.5 2.8 1.7 7.4 9.5 2.0 8.0 4.7 12.7 7.1 24.3 17.6 Table
8 Quantitation of triacylglycerols (wt% on oil) in olive oil heated at 180C for
5, 10 and 15 hours Heating time (h) Non polar TAG POP PLP POS POO POL
SOO OOO SOL OOL 0 95.6 3.3 1.1 1.2 23.2 5.9 5.0 41.5 4.0 9.1 5 85.4 3.3
0.9 1.2 21.4 5.0 4.5 37.1 3.3 7.2 10 77.2 3.2 0.9 1.1 20.2 4.2 4.3 33.7 2.9
5.6 15 69.2 3.0 0.8 1.1 18.5 3.5 3.9 30.1 2.6 4.4 Table 9 Quantitation of
triacylglycerols (wt% on oil) in sunflower oil heated at 180C for 5, 10 and
15 hours Heating time (h) Non polar TAG) POP PLP POS POO PLS POL PLL
SOO OOO SOL OOL SLL OLL LLL 0 96.4 0.3 1.1 0.3 2.0 1.3 6.5 9.7 1.3 5.4 3.6
10.9 7.0 25.5 21.5 5 82.8 0.2 0.8 0.3 2.0 1.2 5.8 8.3 1.2 5.4 3.2 10.0 5.7
21.5 17.1 10 73.4 0.3 0.9 0.4 1.9 1.1 5.4 7.2 1.2 5.0 3.1 9.0 5.2 18.4 14.0 15
64.6 0.3 0.8 0.3 1.8 1.1 4.8 6.1 1.3 5.0 3.0 8.2 4.6 15.7 11.4 Table 10
Apparent and quantitative loss of unsaturated triacylglycerols (%) in olive
and sunflower oils heated at 180C for 10 hours Oil Loss POP PLP POS POO
PLS POL PLL SOO OOO SOL OOL SLL OLL LLL Olive Apparent 0 0 0 0 11.3
0 0 9.5 24.2 Quantitative 3.0 18.2 8.3 12.9 28.8 14.0 18.8 27.5 38.5
Sunflower Apparent 0 0 0 0 0 0 3.0 0 0 0 0 2.7 5.3 14.8 Quantitative 0
18.2 0 5.0 15.4 16.9 25.8 7.7 7.4 13.9 17.4 25.7 27.8 34.9 grasas y aceites,
63 (3), julio-septiembre, 284-289, 2012, issn: 0017-3495, doi:
10.3989/gya.034412 289 Apparent and quantitative loss of fatty acids and
triacylglycerols at frying temperatures of the pairs PLP/POO, POL/OOO or
SOL/OOO in olive oil and of PLP/POO, PLS/POO, POL/OOO, SOL/OOO, PLL/OOL
or SLL/OOL in sunflower oil. To sum up, the following conclusions can be
made from this study: 1. From the normalized composition, losses of fatty
acids or TAG during heating of oils cannot be deduced because a significant
part of the sample does not elute in the GC analysis. 2.Quantitative
changes in FAME clearly demonstrated that at the levels of polar compounds
close to 25% in oils heated at frying temperature, all the unsaturated fatty
acids had undergone significant degradation. Their relative loss depended
on both their concentration in the oil and their degree of unsaturation.
However, saturated fatty acids remained at their initial levels. 3. By
maintaining constant the level of the major saturated FAME, a measurement
of the thermoxidative degradation can be easily obtained in dependent
samples. 4. The loss of TAG was higher as their number of double bonds
increases and particularly when the most unsaturated acyl group is present
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Franc. Corps Gras 32, 163-164. Dobarganes MC, Prez-Camino MC. 1988.
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Martnez-Force E; Garcs R. 2000. Identification of triacylglycerol species
from highsaturated sunflower (Helianthus annuus) mutants. J. Agric. Food
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esters 2.301. In Standard Methods for the Analysis of Oils, Fats and
Derivatives, 7th ed.; International Union of Pure and Applied Chemistry,
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the Analysis of Oils, Fats and Derivatives, 7th ed.; International Union of Pure
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Recibido: 5/3/12 Aceptado: 27/3/12 Copyright of Grasas y Aceites is the
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GRASAS Y ACEITES, 58 (2), ABRIL-JUNIO, 148-153, 2007, ISSN: 0017-3495

Optimization of analytical methods for the assessment of the quality of fats

and oils used in continuous deep fat frying
By J.A. Navas, A. Tres, R. Bou, R. Codony and F. Guardiola*
Nutrition and Food Science Department-CeRTA, Faculty of Pharmacy,
University of Barcelona, Av. Joan XXIII, s/n,
08028 Barcelona, Spain.
fguardiola@ub.edu - Francesc Guardiola
N
Optimizacin de mtodos analticos para la evaluacin
de la calidad de grasas y aceites utilizados en el
proceso de fritura en continuo.
La aplicabilidad, repetibilidad y capacidad de diferentes

mtodos de anlisis para discriminar muestras de aceites

con diferentes grados de oxidacin fueron evaluadas mediante
aceites recogidos en procesos de fritura en continuo
en varias empresas espaolas. El objetivo de este trabajo
fue encontrar mtodos complementarios a la determinacin
del ndice de acidez para el control de calidad rutinario de los
aceites de fritura empleados en estas empresas.
La optimizacin de la determinacin de la constante dielctrica
conllev una clara mejora de la variabilidad. No obstante,
excepto en el caso del ndice del ATB, el resto de mtodos ensayados mostraron una menor variabilidad. La
determinacin del ndice del ATB fue descartada ya que su
sensibilidad fue insuficiente para discriminar entre aceites
con diferente grado de oxidacin. Los diferentes parmetros
de alteracin determinados en los aceites de fritura mostraron
correlaciones significativas entre el ndice de acidez y
varios parmetros de oxidacin diferentes, como la constante
dielctrica, el ndice de p-anisidina, la absorcin al ultravioleta
y el contenido en polmeros de los triacilgliceroles. El
ndice de acidez solo evala la alteracin hidroltica, por lo
que estos parmetros aportan informacin complementaria
al evaluar la alteracin termooxidativa.
PALABRAS-CLAVE: Alteracin Control de calidad Fritura
en continuo Grasas y aceites Mtodos de anlisis.