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Flavonoides es el nombre genrico de un grupo de molculas generadas por el

metabolismo secundario de los vegetales, Todos los flavonoides son


estructuras hidroxiladas en el anillo aromtico y, por tanto, son polifenlicas.
Poseen un
carbonilo en posicin 4 y las variaciones se producen en las posiciones 1, 2 y 3
de la
unidad C3 y en el anillo B.

Los flavonoides son compuestos


fenlicos diaril-propnicos, es decir, su estructura es del tipo C6-C3-C6, con dos
anillos
aromticos (bencnicos) unidos entre s por una cadena de 3 carbonos ciclada
a travs de
un oxgeno.

FLAVONOIDES EXCELENTE

Los flavonoides son compuestos de bajo peso molecular


que comparten un esqueleto comn de difenilpiranos
(C6-C3-C6), compuesto por dos anillos de fenilos
(A y B) ligados a travs de un anillo C de pirano
(heterocclico). Los tomos de carbono en los anillos
C y A se numeran del 2 al 8, y los del anillo B desde
el 2' al 6'12 (fig. 1). La actividad de los flavonoides como
antioxidantes depende de las propiedades redox
de sus grupos hidroxifenlicos y de la relacin estructural
entre las diferentes partes de la estructura qumica13.
Esta estructura bsica permite una multitud de
patrones de sustitucin y variaciones en el anillo C.
En funcin de sus caractersticas estructurales se pueden
clasificar en:
1. Flavanos, como la catequina, con un grupo
-OH en posicin 3 del anillo C.
2. Flavonoles, representados por la quercitina,
que posee un grupo carbonilo en posicin 4 y un grupo
-OH en posicin 3 del anillo C.
3. Flavonas, como la diosmetina, que poseen un
grupo carbonilo en posicin 4 del anillo C y carecen
del grupo hidroxilo en posicin C3.
4. Antocianidinas, que tienen unido el grupo
-OH en posicin 3 pero adems poseen un doble enlace
entre los carbonos 3 y 4 del anillo C.
Tres caractersticas estructurales son importantes para
su funcin: a) La presencia en el anillo B de la estructura
catecol u O-dihidroxi; b) La presencia de un
doble enlace en posicin 2,3; c) La presencia de grupos
hidroxilo en posicin 3 y 514. La quercitina presenta las
tres caractersticas, mientras que la catequina solo presenta
la segunda y la diosmetina la primera (fig. 2).
A los flavonoles y las flavonas se unen azcares,
preferentemente a la posicin C3 y con menor frecuencia
al C7 del anillo A, de forma que estos compuestos
se encuentran comnmente como O-glicsidos, siendo
la D-glucosa el residuo azcar ms frecuente. Otros residuos
de azcares son la D-galactosa, la L-ramnosa,
la L-arabinosa, la D-xilosa, as como el cido D-glucurnico.
La parte sin azcares de la molcula flavonoide
se llama aglicona. Los glicsidos son ms solubles
en agua y menos reactivos frente a radicales libres que
su aglicona o flavonoide respectivo.
Las propiedades cido-base muestran que los radicales
flavonoides son neutros en un medio cido (por

Mecanismos prooxidantes
Debido a las caractersticas estructurales de algunos
flavonoides, como las antocianidinas, provocan bajos
potenciales de oxidacin (EP/2), que les permite reducir
el Fe3+ y el Cu2+ para sufrir una autooxidacin o incluso
involucrarse en un proceso de reciclaje redox, actuando
de esta manera como agentes prooxidantes, lo
que explica los efectos mutagnicos y genotxicos de
algunos flavonoides.18
Algunos de estos mecanismos incluyen la reduccin temporal
de Cu (II) a CU (I), la autooxidacin del radical aroxilo
generando anin superxido (O2-) que siguiendo su secuencia
general el daino radical hidroxilo (HO.), as como la
afeccin de las funciones de los componentes del sistema de
defensa antioxidante nuclear: glutatin y glutatin-S-transferasa.
19

Lo que Lo que determina el carcter antioxidante o prooxidante


es la estabilidad/labilidad redox del compuesto radical
formado a partir del flavonoide original (CUADRO FLAVONOIDES)

http://metabolomics.jp/wiki/Category:FL

http://taxonomicon.taxonomy.nl).
Las propiedades cido-base muestran que los radicales flavonoides son neutros
en un medio cido (por debajo de pH 3) y con una carga negativa a pH 7. Las
repercusiones de la carga negativa son sumamente
importantes en la evaluacin del potencial antioxidante
de los flavonoides Primero, el radical
cargado negativamente no es probable que pase a
travs de la membrana celular con carga negativa.
Segundo, la reaccin de los radicales flavonoides
con la vitamina E, que es termodinmicamente factible
para algunos radicales flavonoides, tiene un obstculo
adicional a causa de la repulsin electrosttica
entre el anin del radical flavonoide y la membrana
fosfolipdica cargada negativamente, donde la vitamina
E se incrusta. Tercero, la oxidacin de un slo
electrn de los flavonoides por cualquier oxidante
tendr una barrera entrpica, porque por lo menos
dos protones se intercambian en la reaccin. Los
protones pueden intercambiarse entre los reactantes
o con el solvente en el estado de transicin, en este
caso, la interfase del enlace con hidrgeno debe tenerse
en. cuenta15

Los flavonoides retiran oxgeno reactivo especialmente


en forma de aniones superxidos, radicales hidroxilos,
perxidos lipdicos o hidroperxidos. De esta
manera bloquean la accin deletrea de dichas
sustancias sobre las clulas. Sus efectos citoprotectores
son, por ejemplo, bien patentes en fibroblastos de
la piel humana, queratinocitos, clulas endoteliales y
ganglios sensoriales cultivados en presencia de sulfoxinabutionina, un inhibidor irreversible de la glutatin
sintetasa43. Diversos flavonoides han mostrado su
eficiencia para eliminar los procesos de peroxidacin
lipdica del cido linoleico o de los fosfolpidos de las
membranas, la peroxidacin de los glbulos rojos o la
autooxidacin de los homogeneizados de cerebro44, 45.
Asimismo, se ha comprobado su potente capacidad de
inhibir in vitro la oxidacin de las lipoprotenas de baja
densidad (LDL) por los macrfagos y reducir la citotoxicidad
de las LDL oxidadas46, 47. De hecho, las
poblaciones que consumen productos ricos en flavonoides
estadsticamente presentan menores riesgos de
afecciones cardiovasculares10,

Un antioxidante es una molcula capaz de retardar o prevenir la oxidacin de


otras molculas. La oxidacin es una reaccin qumica de transferencia de electrones de una
sustancia a un agente oxidante. Las reacciones de oxidacin pueden producir radicales
libres que comienzan reacciones en cadena que daan las clulas. Los antioxidantes terminan
estas reacciones quitando intermedios del radical libre e inhiben otras reacciones
deoxidacin oxidndose ellos mismos. Debido a esto es que los antioxidantes son a
menudo agentes reductorestales como tioles o polifenoles. Los antioxidantes se encuentran
contenidos en
el olivo, ajo, arroz integral, caf,coliflor, brcoli, berenjena, jengibre, perejil, cebolla, ctricos,
semolina, tomates, aceite de semilla de la vid, t,romero, entre otras muchas sustancias. La
capacidad antioxidante de algunos frutos, como es el caso de las berenjenas, es mayor
durante sus estadios iniciales.1 Tambin son parte importante constituyente de la leche
materna

Los flavonoides en general se extraen de muestras secas y


molidas. La muestra se
desengrasa inicialmente con ter de petrleo n-hexano, y el marco se extrae
con etanol
puro o del 70%. Este ltimo es recomendado para garantizar la extraccin de
los ms
polares. El extracto obtenido se evapora con calentamiento no superior a los
50C y se le

hacen particiones sucesivas con ter etlico, acetato de etilo y n-butanol. Los
flavonoides
apolares quedan en la fase etrea, los medianamente polares en la fase
acetato de etilo y los
ms polares en el n-butanol

Los flavonoides retiran oxgeno reactivo, especialmente


en forma de aniones superxidos, radicales hidroxilos,
hidroperxidos y perxidos lipdicos. Bloqueando la accin
deletrea de estas sustancias sobre las clulas. Donde
se ha corroborado la proteccin antioxidante de los flavonoides
en: queratinocitos, fibroblastos drmicos, ganglios
sensoriales, endotelio, tejido nervioso y en lipoprotenas
de baja densidad

http://www.hindawi.com/journals/tswj/2013/162750/

Oxidative modification of LDL cholesterol is thought to play a key role during


atherosclerosis. The isoflavan glabridin, a major polyphenolic compound found
in Glycyrrhiza glabra (Fabaceae), inhibits LDL oxidation via a mechanism
involving scavenging of free radicals [52].

Flavonoidspossessmanybiochemicalproperties,butthebestdescribed
propertyofalmosteverygroupofflavonoidsistheircapacitytoactasantioxidants.
Theantioxidantactivityofflavonoidsdependsuponthearrangementoffunctional
groupsaboutthenuclearstructure.Theconfiguration,substitution,andtotalnumber
ofhydroxylgroupssubstantiallyinfluenceseveralmechanismsofantioxidant
activitysuchasradicalscavengingandmetalionchelationability
(http://www.hindawi.com/journals/tswj/2013/162750/)

Flavonoids possess many biochemical properties, but the best described


property of almost every group of flavonoids is their capacity to act as
antioxidants. The antioxidant activity of flavonoids depends upon the
arrangement of functional groups about the nuclear structure. The
configuration, substitution, and total number of hydroxyl groups substantially
influence several mechanisms of antioxidant activity such as radical
scavenging and metal ion chelation ability [4, 67]. The B ring hydroxyl
configuration is the most significant determinant of scavenging of ROS and RNS
because it donates hydrogen and an electron to hydroxyl, peroxyl, and
peroxynitrite radicals, stabilizing them and giving rise to a relatively stable
flavonoids radical [68].

Mechanisms of antioxidant action can include (1) suppression of ROS formation


either by inhibition of enzymes or by chelating trace elements involved in free
radical generation; (2) scavenging ROS; and (3) upregulation or protection of
antioxidant defenses [69, 70]. Flavonoid action involves most of the
mechanisms mentioned above. Some of the effects mediated by them may be
the combined result of radical scavenging activity and the interaction with
enzyme functions. Flavonoids inhibit the enzymes involved in ROS generation,
that is, microsomal monooxygenase, glutathione S-transferase, mitochondrial
succinoxidase, NADH oxidase, and so forth [71].

Lipid peroxidation is a common consequence of oxidative stress. Flavonoid


protect lipids against oxidative damage by various mechanisms [5, 51]. Free
metal ions enhance ROS formation by the reduction of hydrogen peroxide with
generation of the highly reactive hydroxyl radical. Due to their lower redox
potentials flavonoids (Fl-OH) are thermodynamically able to reduce highly
oxidizing free radicals (redox potentials in the range 2.131.0V) such as
superoxide, peroxyl, alkoxyl, and hydroxyl radicals by hydrogen atom donation
(Figure 4(a)). Because of their capacity to chelate metal ions (iron, copper,
etc.), flavonoids also inhibit free radical generation [70, 72]. Quercetin in
particular is known for its iron-chelating and iron-stabilizing properties. Trace
metals bind at specific positions of different rings of flavonoid structures [73].
The binding sites are shown in Figure 4(b).

A 3,4-catechol structure in the B ring firmly enhances inhibition of


lipid peroxidation. This trait of flavonoids makes them most effective
scavengers of peroxyl, superoxide, and peroxynitrite radicals [4]. Epicatechin
and rutin are strong radical scavengers and inhibitors of lipid peroxidation in
vitro [74]. Because of oxidation on the B ring of flavonoids having catechol

group a fairly stable orthosemiquinone radical is formed which is strong


scavengers. Flavones lacking catechol system on oxidation lead to
formation of unstable radicals exhibit weak scavenging potential [75].
The literature shows that flavonoids having an unsaturated 2-3 bond in
conjugation with a 4-oxo function are more potent antioxidants than the
flavonoids lacking one or both features. Conjugation between the A and B rings
allows a resonance effect of the aromatic nucleus that provides stability to the
flavonoid radical. Free radical scavenging by flavonoids is potentiated by the
presence of both the elements besides other structural features [76].

The flavonoid heterocycle contributes to antioxidant activity by permitting


conjugation between the aromatic rings and the presence of a free 3-OH.
Removal of a 3-OH annuls coplanarity and conjugation which compromises
scavenging ability [77]. It is proposed that B ring OH groups form hydrogen
bonds with the 3-OH, aligning the B ring with the heterocycle and A ring. Due
to this intramolecular hydrogen bonding, the influence of a 3-OH is enhanced
by the presence of a 3,4-catechol, elucidating the potent antioxidant activity
of flavan-3-ols and flavon-3-ols that possess the latter feature. Generally Omethylation of hydroxyl groups of flavonoids decreases their radical scavenging
capacity [76].

Occurrence, position, structure, and total number of sugar moieties in flavonoid


(flavonoids glycosides) play an important role in antioxidant activity. Aglycones
are more potent antioxidants than their corresponding glycosides. There are
reports that the antioxidant properties of flavonol glycosides from tea declined
as the number of glycosidic moieties increased [78]. Though glycosides are
usually weaker antioxidants than aglycones, bioavailability is sometimes
enhanced by a glucose moiety. In the diet, flavonoid glycosidic moieties occur
most frequently at the 3- or 7-position [79]. Increasing degree of
polymerization enhances the effectiveness of procyanidins against a variety of
radical species. Procyanidin dimers and trimers are more effective than
monomeric flavonoids against superoxide anion. Tetramers exhibit greater
activity against peroxynitrite and superoxide mediated oxidation than trimers,
while heptamers and hexamers demonstrate significantly greater superoxide
scavenging properties than trimers and tetramers

A 3,4catechol structure in the B ring firmly enhances inhibition of lipid


peroxidation. This trait of flavonoids makes them most effective scavengers of
peroxyl,superoxide,andperoxynitriteradicals[4].Epicatechinandrutinarestrong

radicalscavengersandinhibitorsoflipidperoxidationin vitro[74].Becauseof
oxidation on the B ring of flavonoids having catechol group a fairly stable
orthosemiquinoneradicalisformedwhichisstrongscavengers.Flavoneslacking
catecholsystemonoxidationleadtoformationofunstableradicalsexhibitweak
scavenging potential [75]. The literature shows that flavonoids having an
unsaturated 23 bond in conjugation with a 4oxo function are more potent
antioxidantsthantheflavonoidslackingoneorbothfeatures.Conjugationbetween
theAandBringsallowsaresonanceeffectofthearomaticnucleusthatprovides
stability to the flavonoid radical. Free radical scavenging by flavonoids is
potentiatedbythepresenceofboththeelementsbesidesotherstructuralfeatures
[76].
The flavonoid heterocycle contributes to antioxidant activity by permitting
conjugationbetweenthearomaticringsandthepresenceofafree3OH.Removal
of a 3OH annuls coplanarity and conjugation which compromises scavenging
ability[77].ItisproposedthatBringOHgroupsformhydrogenbondswiththe3
OH,aligningtheBringwiththeheterocycleandAring.Duetothisintramolecular
hydrogenbonding,theinfluenceofa3OHisenhancedbythepresenceofa3 ,4
catechol,elucidatingthepotentantioxidantactivityofflavan3olsandflavon3ols
that possess the latter feature. Generally Omethylation of hydroxyl groups of
flavonoidsdecreasestheirradicalscavengingcapacity[76].
Occurrence, position, structure, and total number of sugar moieties in flavonoid
(flavonoidsglycosides)playanimportantroleinantioxidantactivity.Aglyconesare
morepotentantioxidantsthantheircorrespondingglycosides.Therearereportsthat
theantioxidantpropertiesofflavonolglycosidesfromteadeclinedasthenumberof
glycosidic moieties increased [78]. Though glycosides are usually weaker
antioxidants than aglycones, bioavailability is sometimes enhanced by a glucose
moiety.Inthediet,flavonoidglycosidicmoietiesoccurmostfrequentlyatthe3or
7position[79].Increasingdegreeofpolymerizationenhancestheeffectivenessof
procyanidinsagainstavarietyofradicalspecies.Procyanidindimersandtrimersare
more effective than monomeric flavonoids against superoxide anion. Tetramers
exhibitgreateractivityagainstperoxynitriteandsuperoxidemediatedoxidationthan
trimers,whileheptamersandhexamersdemonstratesignificantlygreatersuperoxide
scavengingpropertiesthantrimersandtetramers
The precondition to their radical scavenging effect is the number and location
of phenolic groups.2 For example the ortho-dihydroxy (catechol) substitution
raise the radical scavenging activity.3 However, the synthesis of these complex
compounds is complicated given that the selective transfer of oxygen atoms to
non- or little activated carbons is still a challenging reaction in chemical
synthesis.4 (reaccion flavonoide-aromatico)

HEAVY CRUDE OIL VISCOSITY REDUCTION


Taking blending for an example, typically the crude oils are blended with a kerosene distillate
fraction. This process has its disadvantages. In some cases up to 30 wt.% of kerosene must be
added to sufficiently reduce the viscosity, this uses up a great quantity of a valuable commercial
product. Also the added kerosene must be processed again through the refinery along with heavy
crude oil.
It is widely assumed that the asphaltene molecules in oils agglomerate
to form micelle-like clusters. The kerosene used to cut the oils and reduce viscosity

only does so by being an effective diluent. It does not break down the agglomerates by any
significant amount.
The intention is to then augment the better of these additive compounds with kerosene, thus
initiating viscosity reduction for less volume of diluent.

The presence of PI electrons in the ring may play a role in the


interaction between the compounds added and the n electrons in the polyaromatic systems
of the
asphaltene agglomerates. The compounds were kept to one ring to keep the size of the
molecules
small and allow for a greater diffusion through the crude oil matrix, and penetration
into the
asphaltene agglomerates.

In other words the mixture exhibited signs of a Newtonian fluid.

augment

The major general trend to note is that with the


increasing polarity of the dispersant there is an increase in the measured viscosity
which in turn binds the molecules together and hence

increases viscosity. The viscosity reduction however may not just be related to the
break down of
the asphaltene agglomerates. A more simple answer may be related to Eyrings theory
of liquid
viscosity (5).
polarities
between 1 and 3 DU. Therefore, partial solubility must be the cause for the lower measurements.
However, solubility experiments should be conducted to prove this hypothesis

then molecular size of the


additive compound may have an important role in viscosity reduction. Smaller
molecules or
molecules with the correct physical and chemical characteristics to fit into the gaps
between the
asphaltene agglomerates can reduce the viscosity to a greater extent. This is caused by
deeper
penetration, which induces greater break up of the asphaltene agglomerates.

They ascribe this effect to pp 170


interactions and the formation of hydrogen bonds between the 171
functionalized molecule and the asphaltenes, which lowers the 172
asphaltene aggregate size and reduces the viscosity of the crude

ARCHIVO DEL CRUDO IRAQUI

by reducing its viscosity from break down asphaltene


agglomerates using different types of hydrocarbon and oxygenated polar solvents
such as toluene, methanol, mix xylenes, and reformate