Descrioci

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Descrioción anatómica del caracol Purpura
panza,empleado Por los tejedores mixtecos
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Source Natural Synthetic Organic
Inorganic Vegetal, Animal, Microbial 1856.
Discovery of mauve by Perkin (purpure of
Tyre) 1906. review of 80 commercial products (30
never tested before, 26 with mixed results. Only
7 were approved.
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Impact of Biotechnology on the current colorant
Industry
Microbial processes Monascus purpureus
(polyketide pigments) Phaffia rhodozyma
(Astaxanthin) Spirulina maxima
(Phycyanin) Dunallella salina (b-carotene) Extra
ction from seeds and flowers Marigold flowers
(lutein) Crocus sativus (saffron a
crocin) Bixa orellana (achiote) Extraction from
waste products crawfish, red crab, shrimp
(Astaxanthin) Enzymatic process resolution of
zeaxanthin Tissue culture Lithospermum
eryhrorhizon (shikonin) Genetic
Engineering Escherichia coli (indigo)
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CAROTENOIDES

• Uno de los grupos de pigmentos naturales mas
  distribuidos y diversos en la naturaleza. gt600
  estructuras conocidas.
• Algunas especies los sintetizan de novo mientras
  que otras, particularmente animales, solo capaces
  de absorberlos y metabolizarlos.
• Síntesis en la naturaleza de unos 100 millones de
  toneladas anuales
• Carotenos C40 cadenas hidrocarbonadas
  (generalmente anaranjados a rojizos)
• Xantophylls Sus derivados oxigenados
  (generalmente amarillos)
• De los conocidos, un 10 tiene valor como
  vitamina A . Además del beta-caroteno, los más
  importantes entre ellos son el alfa-caroteno y la
  b eta-criptoxantina. La condición fundamental
  para que tengan actividad vitamínica es que
  tengan cerrado y sin oxidar al menos uno de los
  anillos de los extremos de la estructura.
• Licopeno, zeaxantina y luteína no tienen valor
  como vitamina A, aunque son muy importantes como
  pigmentos, y pueden tener también actividad como
  antioxidantes.

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Annato (Bixa orellana L)
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Bixin (Apocarotenoide) Achiote (Mexico),
Urucum (Brasil). también roucou, onato, bija,
orlean, Extracción tradicional en proceso
acuoso a alta temperatura Bixin es soluble en
grasa pero no en agua tratada con alcali, Se
hidroliza el ester metílico para producir
norbixin, (dicarboxilic) que es soluble en agua.
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Method of removing pigment from annatto seed
United States Patent 4204043 EXAMPLE Bixa
seeds (36 seeds, approximately 2.5 g), harvested
one day earlier near San Isidro, Costa Rica,
Placed in a 250 ml flask with 60 ml of water
and 0.1 g of Spark-L (a pectinase produced by
Miles Laboratories, Elkhart, Ind., containing
polygalacturonase and pectinesterase). The
flask was stirred occasionally over a period of
18 hours at ambient temperature (22-25 C.).
The contents of the flask had a good odor with
no indication of fermentation having occurred.
The aqueous dispersion of the annatto was
decanted from the seeds. As a control, the
procedure described above was repeated without
addition of enzyme. Removal of Pigment
Treatment From Seed () Water pectinase 70
Water (control) 10
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Astaxantina (4-5 veces más eficiente) Astaxanthin
is produced by microalgae, yeast, salmon, trout,
krill, shrimp, crayfish, crustaceans, and the
feathers of some birds. 2000-4000 US/Kg Salmón
35-75 mg/Kg alimento (10-15 costo dieta)
astaxanthin
MERCADO DE ALGUNOS CAROTENOIDES
capsanthin
b-Caroteno sintético 750 US/Kg natural 180
0 US/Kg
ß-carotene
Cenpazuchil
lutein
zeaxanthin
                                              
                                              
Cantaxantina 1500 US/Kg
canthaxanthin
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Amounts of astaxanthin found in different
organisms7
Natural Astaxanthin Sources Astaxanthin Concentration(ppm)
SalmonidsPlanktonKrillArctic shrimpPhaffia YeastHaematococcus pluvialis 5 60 120 1200 800040,000
Haematococcus pluvialis (0.5-2 dry
weight) Phaffia rhodozyma Adonis aestivalis
(200-350 mg/flower) Brevibacterium lacticola
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• INDIGO
• The world largest selling textile dye (by vol)
  13, 000 ton/year with a value of 200 million
  dollars.
• From Mollusks genus Murex
• European woad plant Isatis tinctoria
• Asian Indigofera tinctoria
• 1883 Adolf von Baeyer (chemical structure) Nobel
  prize.
• 1897 BASF---? chemical synthesis
• Genencor recombinant E. coli with 9 genes cloned.
• Genencor indigo more expensive than synthetic
  product

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Cochineal the best natural pigment (carminic
acid)
Insects of the families Coccoides Aphidoides
Porphyropera hameli (Armenian Re) grows in
grasses of Azerbaijan Kermococcus
vermilis (Kermes grows in oaks) Margarodes
polonius (roots of a grass in various trees in
India Malaysia) Dactylopius coccus (cacti
Opuntia)
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80,000 100,000 insects/Kg of raw dried
cochineal (22 of their dry weight) Todays
production only a small fraction of thet in
XVI-XIX centuries (eg. Canary islands alone
produced 3000 ton in 1875). Extracted with hot
water Treatment with protease -----? carmines
of cochineal. Strawberry ?----? blackcurrent.
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• According to the World Health Organization,
  dietary vitamin A deficiency (VAD) causes some
  250,000 to 500,000 children to go blind each
  year. More than half those who lose their sight
  die within a year. VAD compromises the immune
  systems of approximately 40 percent of children
  under five in the developing world, greatly
  increasing the risk of severe illnesses from
  common childhood infections. VAD is most severe
  in Southeast Asia and Africa.
• has become a staple food in many African
  countries. Globally, rice grain is the world's
  most important source of human food-feeding more
  than half of the world's population. Rice is a
  good provider of calories and protein, but rice
  scientists have long recognized its micronutrient
  deficiencies. Milled white rice contains
  essentially no beta-carotene and unmilled brown
  rice contains a very small amount.
• Public rice research institutions in the
  Philippines, Vietnam, India, Bangladesh, China
  and Indonesia are in various stages of leading
  efforts to develop locally adapted Golden Rice
  varieties.

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LOS PARADIGMAS
En el arroz no se expresa la Fitoeno sintasa. La
primera variedad tenía el gene del narciso y la
fitoeno desaturasa de la bacteria Erwinia
pseudonarcissus. La nueva variedad tiene la
sintasa del maíz y contiene mas de 30mg de
b-caroteno por g de arroz.
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lycopene
More than 250 million sub-Saharan Africans rely
on the cassava, a starchy tuber native to South
and Central America, as their staple food.
Cassava supplies 38.6 of the caloric
requirements in some parts of Africa, where
hunger and nutrient deficiencies grip the
populace and more than 40 of global cassava
production takes place.
Launched in July 2005 with 7.5 million from the
Bill and Melinda Gates Foundations Grand
Challenges in Global Health Initiative, the
programs overarching goal is to develop what
essentially amounts to a super-charged cassava
plant varietyone with increased levels of iron,
zinc, protein, vitamins, and resistance to the
cassava mosaic and brown streak viruses plaguing
African farmers.
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Cassava ß-Carotene is a dietary precursor of
vitamin A that is synthesized by the
methylerythritol phosphate (MEP) pathway in
plastids of some plant cells. Conventional
cassava roots lack some of the essential enzymes
necessary to produce ß-carotene. The initial step
in the pathway is controlled by
deoxyxylulose-5-phosphate synthase (DXS), which
is added to Cahoons cassava via the gene dxs ,
originally sourced from a different plant
species. Additional steps generate the C5
isopentenyl diphosphate (IPP) that is used as the
building block for the synthesis of the C20
geranylgeranyl diphosphate (GGDP). Phytoene
synthase (PSY), the product of an introduced gene
(psy) from a bacterial source, combines two
molecules of GGDP to form phytoene, which is
converted to ß-carotene via lycopene through a
series of desaturation, isomerization, and
cyclization reactions. The end result is a
noticeably more orangey cassava root.
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Arabidopsis gene, 1-deoxy-d-xylulose 5-phosphate
synthase (dxs), which regulates the isoprenoid
pathway, a set of biochemical reactions further
upstream from the biosynthetic step in which psy
is involved. Inserting dxs, which increases the
amount of chemical precursors to beta-carotene,
was like turning up the whole isoprenoid
pathway, Cahoon says. He found that inserting
both the psy and dxs genes resulted in a cassava
even more orange than the roots with only the psy
modificationand with 30 times more beta-carotene
than normal roots.
The BioCassava Plus program has also recently
seen significant progress in its goal to
introduce biofortified foods into the developing
world. Director Richard Sayre says that the
programs pro-vitamin A cassava plants have been
approved for field trials in Nigeria, the worlds
number one consumer of the food. In July, the
country planted between 4000 and 8000 m2 with
Cahoons two-gene GM cassava, the first GM
product Nigeria has field tested. We are quite
proud of that, Sayre says. To advance the
BioCassava Plus program to the next stage, Sayre
says that more donor money will be needed. He
says that the program is planning on approaching
other donors, but declined to name them.
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0
Capsaicinoids (15) Carotenoids (0)
Aqueous enzymatic treatment
Capsaicinoids (44) Carotenoids (2)
30 Ethanol extraction
96 Ethanol extraction
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Capsaicinoides

• Compuestos causantes de la pungencia en los
  chiles (Capsicum annuum).
• Estimulantes en el tracto digestivo,
  bloqueadores de la transmisión del dolor y
  promueven el metabolismo energético.
• Aplicaciones Condimentos alimenticios,
  industria del tabaco, repelentes de protección
  personal y en compuestos para la agricultura,
  pinturas marinas, medicamentos contra el dolor.

Capsaicina
Santamaría R., Reyes Duarte M.D., Barzana E.,
Fernando D., Gama F.M., Mota M. Lopez- Munguía
A., Journal of Agricultural and Food Chemistry,
48, 7, 3063-3067, 2000.
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Estructura de los capsaicinoides y su pungencia
Generalidades

•  
• Análisis sensorial medido en unidades Scoville
• Cuantificación en ppm por HPLC
• Modelo de Jancsó-Gabor

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Conversión de capsaicina en agua utilizando
diferentes enzimas
Resultados
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Reacción de hidrólisis de la capsaicina
Reyes- Duarte D., Castillo E. Bárzana E.
López-Munguía A. Biotechnology Letters. 22
1811-1814, 2000.
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Síntesis de N-vainillíl oleamida Efecto de la
amina terciaria
H
C
O
H
C
O
3
3
l
C
H

N

N
H
O
N
H
H
O
N
H

H
C
l
2
2
V
a
i
n
i
l
l
i
n
a
m
i
n
a
D
I
P
E
A
H
C
O
O
3
A
c
i
d
o

o
l
e
i
c
o
N
H
O
L
i
p
a
s
a

B

d
e

H
C
a
n
d
i
d
a

a
n
t
a
r
c
t
i
c
a
N-Vainillíl oleamida (olvanil)
Reyes D.D., Castillo E., Martinez R. López
Munguía A. Biotechnology Letters 24, 2057-2061.
2002.
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Síntesis enzimática de capsiato en un solo
sistema

• Alcohólisis
• Hidrólisis y síntesis

Vainillinalcohol
Lipasa B de Candida antarctica
Capsaicina
Capsiato
Vainillinamina
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Efecto de la capsaicina y sus derivados en el
canal de calcio T de células espermatogénicas y
la relación con su pungencia

• Sensorialmente, la capsaicina es pungente, su
  hidrolizado no, ni tampoco el capsiato.

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Síntesis de Análogos de la Capsaicina
Síntesis de amidas con altos rendimientos (gt80)
en 2M2B (solvente polar) independientemente de
la estructura del análogo. 2 análogos con
actividad pungente
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Análogos de capsaicina inhibidores de canales
Ca2 T-type
Síntesis de Capsiato
Síntesis de Olvanil
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Evaluación farmacológica (Colaboración con
Alberto Darszon e Ignacio López)
inhibidores de canales Ca2 T-type
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Síntesis quimoenzimaticadel Fenil-acetil-rinvanil
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