Composizione chimica e proprietà nutraceutiche
dei semi di canapa: un alimento antico con valori funzionali attuali
Dipartimento di Scienze e TecnologieAmbientali Biologiche e Farmaceutiche
15 febbraio 2019 Prof.ssa Severina [email protected]
Fiera Internazionale della Canapa, Canapa Mundi, Roma F C LUniCampania
FoodChemLab
Cu
rren
t p
op
ula
tio
n
health trends
nutrition ⇢improvement of overall well-being
Well-being coincides with the search for a benefit, for which food is a means not only
to pursue sensory and emotional pleasure, but also to preserve physical health
The interest in health promotion and safeguard has reached a greater degree of scientific and institutional attention
When this connotation has a very marked character, it can be claimed as functional food.
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functional foodsfoods or dietary components that may provide a health benefit beyond basic nutrition
foods that by virtue of physiologically active food components provide health benefits beyond basic nutrition
similar in appearance to a conventional food, consumed as part of the usual diet, with demonstrated physiological benefits, and/or to reduce the risk of chronic disease beyond basic nutritional functions
Food fortified with added or concentrated ingredients to functional levels, which improve health and performance
functional
FOOD HEALTH BENEFITS
reduced risk of disease
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“any substance that may considered a food or part of food and provides medical or health benefits, including the prevention and treatment of disease. Such products may range from isolated nutrients, dietary, supplements and diets to genetically engineered ‘designer’ foods, herbal products, and processed foods such as cereals, soups, and beverages”
Nutraceutical
Nutrition +
PharmaCeutical
defence strategyplant’s defence against external aggressions UV irradiation,
microbial attacks, insect feeding deterrent, etc
visual ecological markers in flowers and fruits e.g. attract pollinators and animals for seed dispersal
bioactives for humans
health effects
sensory properties
antioxidant
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dietary seeds represent one of the richest source of nutraceuticals of the modern diet
Salvia hispanica L.
chia seeds high content in essential fatty acidsappreciable amount of phenol antioxidantsalternative to improve consumer’s health
Linum usitatissimum L.
flaxseeds
sc= seedcoatem= embryo secoisolariciresinol
diglucoside
herbacetin in its diglucoside form
Avena sativa L.
oat seeds
avenanthramides (AVAs)antioxidant
anti-inflammatoryantiproliferative
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Class - AngiospermaeSubclass - DicotyledoneaeOrder - UrticalesFamily - CannabaceaeGenus - CannabisSpecies - Cannabis sativa L.
Humulus lupulusCannabis sativa
Fiber hemp plants
Oilseed plants
Intoxicant plants
Phytochem Rev (2008) 7:615-639
Cannabis sativa L. is one of the earliest cultivated plant species, with a long and troublesome history, which strictly intertwines that of humans
use denial
survival
multi-purpose crop
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Scientific name and primary traits
Genome group Origin and diffusion (→) Common uses
C. sativa ssp. sativa
raramente psicoattivaResina bassaCBD=THC (1:1)
NLHNarrow leaflet hemp
Europe→ New World
Fiberand seed
THC ≤ 0.3%
C. indica ssp. chinensis
mediamente psicoattivaResina moderataCBD=THC (1:1)
BLHBroad Leaflet hemp
East Asia→ Europe→ New World
Fiberand seed
THC ≤ 0.5%
C. indica ssp. indica
Molto psicoattivaResina moderataCBD<THC (1:20)
NLDNarrow leaflet drug
South Asia→ Middle East→ Africa→ Europe→ New World
DrugFiber and seed
THC ≤ 20%
C. indica ssp. afghanica
moderatamente psicoattivaResina altaCBD=THC (1:1)
BLDBroad Leaflet drug
Afghanistan→ Europe→ New World
DrugTHC ≤ 10%
Hemp cvsCBD>THC (3:1)
NLH × BLH Europe→ New World
Fiberand seed
THC < 0.5%
Sinsemilla cvsvariabilmente psicoattivaResina copiosa
NLD × BLD New World→ Europe→ Worldwide
DrugTHC < 0.1% to > 20%CBD < 0.1% to > 20%
Indica – erroneamente chiamata «sativa»
Afghan – erroneamente chiamata «indica»
THC cvs THC > 20%; CBD < 1.0%CBD cvs THC < 5.0%; CBD ≥ 4.0%
21 st century Cannabis taxonomy
hybrids genomes
geno
me lan
draces
C. in
dic
a s
ub
spec
ies
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seed
branch
leaf
root
flower
fruit
Cannabinoids content
high concentration
low concentration
null concentration
very low concentration
guilty of the Hemp Middle Age… F C LUniCampania
FoodChemLab
seed-membrane
fruit-membrane
shell
light-grey/green2.0-3.5 mm
True seed is enclosed within the pericarp, which forms
the protective hull or shell.
Most of the seed is filled by an embryo, principally the two cotiledons, which are rich in oils, proteins and carbohydrates.
A rudimentary nutritive tissue (endosperm, rich in aleuron bodies) is also present
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In Europe hemp seed was a famine foodfoxtail millet
broomcorn millet
rice
barley
until the 10th century
hempseed
Chinese tombs
employed
for at least 3000 years
on
e o
f th
e fi
ve g
rain
s o
f an
cien
t C
hin
a
food for both humans and livestock
British medieval hemp eeds
▪ The whole seed, including the hull, was eaten.
▪ Crushed peanut-butter type preparations have been produced from hempseed for centuries.
▪ The interest in producing commercial hulled hempseed for culinary purposes dates back only to about 1990.
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analgesic
hempseed pill
vs pulmonary diseases, anemia, gastric catarrh, scrofula, neurasthenia, asthenia, emaciation
in some areas of Southeast Asia
anci
ent
emp
loym
ent
as f
oo
dgrinding the seed in water
hull removal hempseed milk heating*
*until the proteins solidified into curds
butter type solid masspressing
uses for medicinal purposes
35.7% fructus cannabispurgative and hypotensive effect
for sores and skin diseases
coughs jaudicecolic
blood problems
for treating…
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FoodChemLab
▪ 19th-20th centuries – in Russia the seed oil was employed for making soap, paints, varnishes
▪ Lighting oils (replaced by kerosene)
▪ 20th century usually employed as wild bird and poultry feed
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hemp seeds
cold pressing
oil seeds
hulling
hulled hemp
mixing
hemp butter
hemp cake
grinding
hemp meal
bake
hemp crispbread
Hempseed oil is commonly removed
mechanically by cold-pressing, which
provides hempseed cake as
by-product. This latter contains various
amounts of remaining fat. Oil
extraction could be achieved also using
heat or solvents. An expeller or a meal
with lower fat content is obtained.
hempseed cake
Hulled hemp seed, which is the whole seed with the crunchy outer shell removed, comes by quite a few names like hemp hearts, shelled hemp seed and hemp nut. Hulled seed was created essentially to make eating hemp seed more appealing and easier to eat.
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Whole seed Seed meal
Oil 35.5 11.1
Protein 24.8 33.5
Carbohydrates 27.6 42.6
Moisture 6.5 5.6
Ash 5.6 7.2
Energy (kJ/100g) 2200 1700
Total dietary fiber 27.6 42.6
Digestible fiber 5.4 16.4
Non-digestible fiber 22.2 26.2
Typical nutritional content (%) of hempseeda
acv Finola
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Callaway, J.C. Euphytica (2004) 140: 65.
Amino acid Wheat (14%) Soy bean (32%) Hemp seed (25%) Egg white (13%)
alanine 0.50 1.39 1.28 0.83
arginine 0.61 2.14 3.10 0.68
aspartic acid 0.69 3.62 2.78 1.23
cystine 0.28 0.54 0.41 0.29
glutamic acid 4.00 5.89 4.57 1.67
glycine 0.71 1.29 1.14 0.50
histidine* 0.27 0.76 0.71 0.28
isoleucine* 0.53 1.62 0.98 0.74
leucine* 0.90 2.58 1.72 1.08
lysine* 0.37 1.73 1.03 0.74
methionine* 0.22 0.53 0.58 0.47
phenylalanine* 0.63 1.78 1.17 0.76
proline 1.53 1.65 1.15 0.50
serine 0.70 1.54 1.27 0.92
threonine* 0.42 1.35 0.88 0.58
tryptophan* 0.51 0.41 0.20 0.20
tyrosine 0.40 1.14 0.86 0.46
valine 0.61 1.60 1.28 0.98* essential
Typical protein content (%) of each food is reported in brackets
Individual amino acid valuefor each food is given in g per 100 g
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albuminedestin
opened flexible structure closed non-flexible structure
Seven edestin forms have been identified from the seed of the most known Italian hemp variety Carmagnola. They belong to a multigene family with two distinct types of edestin.
aids in DNA repair at a cellular level.
high digestibility (88%–91%)
compatible with the human digestive system
closely resembles the globulin in blood plasma
Hemp seeds can contain up to 36% protein
hemp seed protein is free of the tryspin inhibitors which block protein absorption that is found in abundance in soy. Hemp protein is also free of oligosaccharides found in soy, which cause stomach upset and gas.
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Docimo et al., 2014. Plant Physiol Biochem. 2014;84:142-148.
Wabs (water absorption) decreased, observed as the level of hemp flour increased, could be attributed to the dilution of gluten–protein fractions of wheat flour, responsible for water binding during dough mixing at 30 °C.
Increasing hemp flour level, bread volume was also impaired in comparison with the control
Formulation with the increasing amount of hemp flour yielded bread crumb, characterized by decreasing cohesiveness and increasing chewiness.
Appearance of cross-section of bread a. Control breadb. Bread with 5% of hemp flourc. Bread with 10% of hemp flourd. Bread with 20% of hemp flour
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Pojić et al., Journal of Food Quality38(2015) 431–440
Typical fatty acid profiles (%) of hemp and other seed oils
5 8 7 6 5 4 10 15
2 3 1 3 11 < 1 4 0
9 11 11 15 22 60 23 76
56 55 48 15 63 23 55 8
22 21 13 61 < 1 13 8 < 1
4 1 17 0 0 0 0 0
2 < 1 3 0 0 0 0 0
2.5 2.7 4.1 0.2 > 100 1.8 6.9 > 100n6/n3 ratio
black currant linseed sunflower rapeseed soy olive
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Callaway, J.C. Euphytica (2004) 140: 65.
80-90 g/100 g total FA
Δ6-desaturase
EPA
DMGLA PG-1
52-62%
12-23%
processing storage age of the samples
variability of the fatty acid profile
LNA18:4ω3Stearidonic
acid
20:4ω3Eicosatetraenoic
acid
20:5ω3EPA
22:5ω3Clupanodonic acid
22:6ω3docosahecaenoic
acid (DHA)
LA18:3ω6γ-linolenic
acid
20:3ω6Dihomo-
γ-linolenic acid
20:4ω6arachidonic
acid (AA)
22:6ω6adrenic acid
22:5ω6docosapentaenoic
acid
PG1
PG2
PG3
promotes the AA retention within the cell membrane
out of the cell membrane
+ platelet aggregation+ inflammation
Proper ratios of fatty acids provide proper amounts of prostanoids and leukotrienes which have anti-thrombotic, anti-vasoconstrictive and anti-inflammatory properties
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blood cholesterol levels
blood pressure
insulin dependence in diabetics
tumor growth
cancer
fat metabolism
membrane fluidity
metabolic rate
anti-inflammation status
The benefits of ω-3 PUFA are not only
present when taken in large quantities but the
regular intake of recommended levels (2-2.5%
of caloric intake/day) can be sufficient to
provide many of its nutritional qualities.
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Extraction methods employed otherwise affect oil content and its recovery and quality
Cold-pressing CO2 Extraction Soxhlet Extraction
preserve antioxidant substances…
triacylglycerols (TAG)
Hemp seed oil
tocopherolspolyphenolsfree fatty acidspigments
dietary minerals
phytosterolsvitamins
Non-TAG or unsaponifiable fraction
β-sitosterol
campesterol
Δ5-avenasterol15.1
8% o
f H
SO u
n-s
apo
nif
iab
le m
atte
r (1
.84-
1.92
%)
cholesterol absorption via crystallization and co-precipitationPLASMA
Intestinal lumen cholesterol solubility by excluding it from micelles
cholesterol absorption
effective in cholesterol uptake inhibition
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Vit
amin
E v
itam
ers
chain-breaking antioxidant
HS vitamins and minerals mg/100 g
Vitamin E 90.0
Thiamine (B1) 0.4
Riboflavin (B2) 0.1
Phosphorous 1160
Potassium 859
Magnesium 483
Calcium 145
Iron 14
Sodium 12
Manganese 7
Zinc 7
Copper 2
The ratio between the tocopherols in hemp seed oil was found as 5:2:90:3 for α/β/γ/δ-tocopherol, respectively.
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Carotenoids and chlorophyllsThe intensive dark green color feature of hempseed oil is associated with the high content of total chlorophylls, which can have many adverse effects…
1. chlorophylls are susceptible to photo-oxidation under the exposure of light, which causes the color change of the oil from dark green to yellow.
2. the high content of chlorophyll could give rise to the instability of free fatty acids in the oil, accelerating the rancidity and result in a rancid aroma.
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JUSO-31
Carmaleonte*
Finola
Finola dehulled
UAM
n-hexane
ethanol
+
UAM
UAM = Ultrasound Assisted Maceration
Exploiting the nutraceutical value of hempseed oils…
*hemp variety for fiber production of monoecious type, derived from C. sativa cv. Carmono[Carmagnola x Ermes] x Chamaelon
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UV-Vis spectra in the wavelength range 250-750 nm of oil samples: (a) CsC; (b) CsJ; (c) CsF; (d) CsFd. In the grey box the UV-Vis spectrum of the reference cold-pressed commercial oil is reported. Carotenoid region is underlined in orange, whereas chlorophyll in green.
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A) 1H-NMR and B) 13C-NMR spectra in CDCl3 of hempseed oil
through UAM in n-hexane of commercial hemp seeds previously grounded. ALA = α-linolenic acid; LA = linoleic acid; OA = oleic acid.
TIC chromatogram recorded in negative ion mode of hempseed oil through UAM in n-hexane of commercial hemp seeds. ALA = α-linolenic acid; GA = gadoleic acid; LA = linoleic acid; OA = oleic acid; PA = palmitic acid; SA = stearic acid; SDA = stearidonic acid. Peaks not assigned are not fatty acid compounds.
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ω6/ω3 ratio of UAM oils and commercial cold-pressed oil
JUSO-31
Carmaleonte
Finola
Finola dehulled
Finola
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Peak n. Rt
(min)Tentative assignment
Formula
[M-H]- found
(m/z)
[M-H]- calc.
(m/z)
error
(ppm)
RDB
MS/MS fragment ions
(m/z)
1 0.304 Tetrahexoside C24
H42
O21
665.2148
701.1915
[M+Cl]-
665.2146
0.3 4 665.2185(100); 485.1509(8.8); 443.1393(5.7); 383.1194(53.0); 341.1070(10.9); 221.0669(8.6); 179.0569(24.7); 119.0358(5.7); 89.0228(7.7)
2 0.320 Trihexoside C18
H32
O16
503.1621
539.1389
[M+Cl]-
503.1618 0.7 3 503.1640(100); 341.1097(11.9); 323.0974(7.8); 281.0851(8.1); 251.0750 (2.0); 221.0666 (54.2); 179.0555(46.5); 161.0455(13.3); 131.0357
(1.4); 119.0347(9.8); 113.0245(14.8); 101.0238(10.9); 89.0244(29.3)
3 2.505 Rutin C27
H30
O16
609.1466 609.1461 0.8 13 609.1498(100); 301.0357(28.6); 300.0276(63.9); 271.0241(41.3); 255.0290(22.5); 243.0294(7.98); 227.0363(2.9); 178.9981(3.2); 151.0031(4)
4 2.783 Hesperidin C28
H34
O15
609.1823 609.1825 1.0 12 609.1858(27.9); 325.0718(6.8); 301.0714(100); 286.0486(11.6); 257.0817(6.2); 242.0568(7.9); 241.0488(4.8); 227.0328(2.1); 214.0638(4.9);
199.0385(5.1); 164.0115(6.7); 151.0028(1.9); 125.0245(2.4)
5 3.088 quercetin-3-O-(6”-O-acetyl)hexoside C23
H22
O13
505.0989 505.0988 0.3 13 505.1008(49.8); 301.0353(27.9); 300.0273(100); 271.0245(60.9); 255.0288 (25.6); 243.0297(17.8); 227.0339(7.9); 211.0380(3.7);
199.0378(5.9); 151.0027(7.8)
6 4.011 trihydroxyoctadecenoic acid C18
H34
O5
329.2330 329.2333 -0.1 2 329.2333(100); 229.1439; 211.1329; 171.1030; 139.1167; 127.1128
7 5.023 dihydroxyoctadecenoic acid C18
H32
O4
311.2227 311.2228 -0.3 3 311.2239(96); 293.2119(16.2); 275.2020(11.7); 235.1714(17.1); 223.1708(100); 87.0462(9.2)
8 5.171 6,7-epoxycannabidiolic acid C22
H30
O5
373.2018 373.2020 -0.7 8 373.2013(95.4); 329.2122(100); 311.2011(67.4); 271.1676(17.7); 259.1675(11.6); 205.1211(28.1); 173.0971(33.4)
9 5.344 dihydroxylinoleic acid C18
H34
O4
313.2383 313.2384 -2 2 313.2375(100); 295.2260(11.2); 277.2152(10.2); 183.1381(66.5); 129.0918(16.1); 99.0807(16.5)
10 5.945 6,7-epoxytetrahydrocannabinolic
acid
C22
H30
O5
373.2020 373.2020 -0.1 8 373.2030(100); 329.2127(46); 311.2022(31.2); 287.2007(5.5); 271.1711(17.5); 259.1701(6.4); 205.1231(23.5); 191.1078(15.8); 179.1076(8.5);
173.0969(28.8); 158.0728(5.6); 123.0815(2.2)
11 6.301 hydroxy linoleic acid C18
H32
O3
295.2279 295.2279 -0.6 3 295.2275(100); 277.2170(74.5); 195.1384(18.8); 171.1024(21.8)
12 6.683 cannabielsoic acid A C22
H30
O5
373.2020 373.2020 0.1 8 373.2040 (43.2); 355.1924(100); 337.1811(11.7); 329.2142(7.6); 311.2017(57.6); 309.1842(17.8); 293.1907(8.9); 291.1767(12.2)
287.1282(40.1); 173.0971(58.5)
13 6.880 6,7-epoxycannabichromenic acid
C22
H30
O5
373.2016 373.2020 -1.2 8 373.2027(100); 329.2116(21.3); 311.2019(41.4); 271.1700(17.3); 205.1235(23.7); 173.0971(21.5); 158.0745(7.1); 137.0956(5.9)
14 7.169 γ-linolenic acid C18
H30
O2
277.2169 277.2173 -1.5 4
15 7.471 cannabielsoic acid B C22
H30
O5
373.2020 373.2020 -0.1 8 373.2042(23.5); 355.1924(100); 329.2120(45.6); 311.2015(35.1); 287.1287(36.8); 271.1704(19.6); 259.1347(14.2); 243.1414(26.4);
205.1238(9.9); 191.1070(22.7); 173.0965(11.0)
16 7.486 cannabidiolic acid C22
H30
O4
357.2076 357.2071 1.3 8 357.2067(100); 339.1958(67.7); 313.2160(34.4); 311.2007(45.8); 295.2073(11); 289.1433(16.9); 271.1329(32.8); 245.1537(82.2);
227.1431(28.2); 203.1071(5.2); 179.1063(25.5); 170.0730(25.8); 137.0968(5); 107.0494(18.7)
17 7.718 stearidonic acid C18
H28
O2
275.2014 275.2017 -0.9 5 275.2013(100); 231.2114(40.3); 203.1772(1.3)
18 8.448 α-linolenic acid C18
H30
O2
277.2176 277.2173 1.4 4 277.2177(100); 259.2072(3.1); 233.2275(2.3); 205.1952(1.3); 127.0758(1.2)
19 9.388 linoleic acid C18
H32
O2
279.2331 279.2330 0.5 3 279.2330(100); 261.2225(4.3)
20 9.68 tetrahydrocannabinolic acid C22
H30
O4
357.2070 357.2071 -0.4 8 357.2082(100); 339.1972(1.8); 313.2186(68.2); 311.2019(11.0); 245.1547(27.1); 229.1243(6.5); 203.1090(11.3); 191.1069(19.1);
179.1070(7.1)
21 10.030 cannabichromenic acid C22
H30
O4
357.2070 357.2071 -0.4 8 357.2082(100); 339.1981(34.5); 313.2164(37.3); 203.1065(17.6); 191.1068(33.8)
22 10.176 oxohexadecanoic acid
(oxopalmitoleic acid)
C16
H30
O3
269.2117 269.2122 -1.9 2 269.2120(100); 225.2235(15)
23 10.206 palmitoleic acid C16
H32
O2
255.2332 255.2330 1.0 1 255.2335(100); 219.8542(7.1); 201.8346(12); 166.8656(13.9)
24 10.520 oleic acid C18
H34
O2
281.2491 281.2486 1.8 2 281.2490(100)
25 11.411 stearic acid C18
H36
O2
283.2643 283.2643 0.2 1 283.2646(100)
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ω-6:ω-3 =2.23
α-linoleic acid
linolenic acid
4.152 mg eq CBD per g oil 11.53x
IA = 2.55 ± 0.23
Cannabidiolic Acid as a Selective Cyclooxygenase-2 Inhibitory Component in Cannabis
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XIC m/z 373.2
TIC
XIC m/z 357.2
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CBD-A
CBG-A
…altro metodo estrattivo…altra cv
ALALA
9831,13
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UAM
n-hexane
defatted hempseed
hempseed oil +
EtOH extract
UAM
ethanol
SiO2
CClignanamide fraction
UAM = Ultrasound assisted
maceration CC = Column
Chromatography
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Trolox®
Trolox®
Cs-EtOAcL/L Cs-EtOAc
L/L
RSC = Radical Scavenging Capacity
DPPH and ABTS methods data…
ID50
= 10.27 μg/mL
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a
a
ccb
dd
e2D NMR hemp seed ethanolic extract
eb
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fen
ola
mm
idi
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lignanammidi1% dei metaboliti del seme
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lignanamide fraction
LC HRMS data of compounds in lignanamide fraction (LF)
UPLC-QTOF- MS total ion chromatogram (TIC) acquired in negative mode
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SH-SY5Y ctrl SH-SY5Y Cs-EtOAcL/L
-treated SH-SY5Y vinblastine-treated
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…clear morphological changes were observed
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Experimental factors tested: i) pre-seeding soil fertilization: Fertilized (F) vs non-fertilized control (NoF); ii) foliar fertilization: foliar fertilized (Fol) vs non-fertilized control (NoFol); iii) crop density: 60 plant m2 (D1) vs 30 plants m2 (D2). The abovementioned factors were fully combined obtaining 8
treatments (F-Fol-D1, F-Fol-D2, F-NoFol-D1, F-NoFol-D2, NoF-Fol-D1, NoF-Fol-D2, NoF-NoFol-D1, NoF-NoFol-D2), each one arranged in a 1200 m2 plot.
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Peak
n.
Rt
(min)
Tentative assignment Formula [M-H]- found (m/z) [M-H]-
calc.(m/z)
error
(ppm)
RDB MS/MS fragment ions (m/z)
1 0.305 Trihexoside C18
H32
O16
503.1629 503.1631 2.3 3 221.0660; 179.0557; 161.0434; 119.0337; 113.0229
2 0.313 Dihexoside C12
H22
O11
341.1092
377.0861 [M+Cl]-
387.1115 [M+HCOO]-
341.1089 0.8 2 179.0566; 161.0466; 149.0446; 143.0321; 131.0386; 119.0345; 113.0244;
101.0345; 89.0244
3 0.327 dihexosyl propanetriol C15
H28
O14
431.1417 431.1406 2.5 2 341.1085; 179.0547; 161.0467; 131.00339; 119.0356
4 0.348 citric acid C6H
8O
7191.0196 191.0197 -0.7 3 111.0093; 87.0082
5 0.331 malic acid C4H
6O
5133.0145 133.0142 1.9 2 115.0039
6 0.460 isocitric acid C6H
8O
7191.0203 191.0197 3.0 3 111.0089
7 1.347 dihydroxybenzoic acid
hexoside
C13
H16
O9
315.0720 315.0722 -0.5 6 153.0202; 152.0128; 109.0287; 108.0228
8 1.456 hydroxytyrosol hexoside C14
H20
O8
315.1079
351.0851[M+Cl]-
315.1085 -2.0 5 153.0562; 123.0451
9 1.874 caffeoyl-tartaric acid
(isomer 1)
C13
H12
O9
311.0409 311.0403 0.1 8 179.0347; 149.0092; 135.0457
10 2.088 caffeoyl-tartaric acid
(isomer 2)
C13
H12
O9
311.0406
623.0896 [2M-H]-
311.0403 -0.8 8 179.0348; 149.0093; 135.0453; 134.0375
11 2.449 hydroxybenzoic acid
hexoside
C13
H16
O8
299.0072 299.0072 -0.1 6 137.0239
12 2.524 caffeic acid hexoside C15
H18
O9
341.0874 341.0878 -1.2 7 179.0347; 135.0453
13 2.566 p-coumaroyl-tartaric
acid (isomer 1)
C13
H12
O8
295.0458 295.0459 -0.5 8 163.0407; 149.0097; 119.0507
14 2.807 dihydroxycoumarin
hexoside
C15
H16
O9
339.0716 339.0722 -1.6 8 177.0189; 133.0291; 105.0337
15 2.984 p-coumaroyl-tartaric
acid (isomer 2)
C13
H12
O8
295.0462 295.0459 2.9 8 163.0404; 119.0506
16 3.102 p-coumaric acid
hexoside
C15
H18
O8
325.0928 325.0929 -0.3 7 163.0393; 119.0499
LC-MS/MS data of polyphenolic and not polyphenolic constituents from hemp oil hydroalcoholic extract (A)
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FoodChemLab
Peak
n.
Rt
(min)
Tentative assignment Formula [M-H]- found
(m/z)
[M-H]-
calc.(m/z)
error
(ppm)
RDB MS/MS fragment ions (m/z)
17 4.207 Dihydrokaempferol hexoside C21
H22
O11
449.1093 449.1089 0.8 11 287.0556; 269.0447; 259.0612; 243.0641; 125.0246
18 6.237 Rutin C27
H30
O16
609.1477 609.1461 2.6 13 609.1501; 301.0356; 300.0278; 271.0252; 255.0307
19 6.264 quercetin-O-hexoside 1 C21
H20
O12
463.0891 463.0882 1.9 12 463.0909; 301.0365; 300.0288; 271.0257; 255.0308; 243.0310
20 6.342 quercetin-O-hexuronide C21
H18
O13
477.0686 477.0675 2.4 13 477.0718; 301.0370; 300.0295; 283.0266; 255.0308; 211.0408; 178.9996; 151.0048;
121.0302
21 6.397 quercetin-O-hexoside 2 C21
H20
O12
463.0895 463.0882 2.8 12 463.0942; 301.0382; 300.0304; 271.0273; 255.0323; 243.0331; 151.0022
22 6.521 kaempferol-O-hexoside1 C21
H20
O11
447.0937 447.0933 1.2 12 285.0406; 284.0340; 257.0474; 255.0307; 229.0508; 227.0357
23 6.918 kaempferol-O-rutinoside C27
H30
O15
593.1517 593.1512 0.9 13 285.0410; 284.0331; 257.0464; 255.0310; 229.0504; 227.0350
24 7.104 N-caffeoyltyramine C17
H17
NO4
298.1091 298.1085 2.0 10 178.0514; 135.0455
25 7.108 isorhamnetin-O-rutinoside C28
H32
O16
623.1839 623.1618 3.4 13 315.0571; 314.0489; 299.0266; 271.0272; 243.0317
26 7.111 kaempferol-O-hexuronide C21
H18
O12
461.0742 461.0725 3.6 13 285.0409; 257.0455; 229.0498
27 7.125 kaempferol-O-hexoside 2 C21
H20
O11
447.0945 447.0933 2.7 12 285.0411; 284.0331; 255.0306; 227.0350
28 7.217 hesperidin/neohesperidin C28
H34
O15
609.1810 609.1825 -2.5 12 301.0718; 286.0486
29 7.389 isorhamnetin-O-hexuronide C22
H20
O13
491.0832 491.0831 0.2 13 315.0524; 301.0370; 300.0289; 271.0261; 255.0310; 243.0307
30 7.684 N-feruloyl tyramine1 C18
H19
NO4
312.1240 312.1241 -0.4 10 190.0506; 178.0506; 148.0530; 147.0450; 135.0448; 134.0358
31 8.039 quercetin 3-O-(acetyl-hexoside) C23
H22
O13
505.0999 505.0988 2.2 13 301.0357; 300.0273; 271.0232; 255.0297
32 8.53 N-feruloyl tyramine 2 C18
H19
NO4
312.1242 312.1241 0.3 10 190.0508; 178.0508; 147.0452; 135.0448
33 8.881 kaempferol hexuronyl methyl
ester
C22
H20
O12
475.0890 475.0882 1.7 13 285.0413; 284.0332; 255.0303; 229.0520; 227.0355
LC-MS/MS data of polyphenolic and not polyphenolic constituents from hemp oil hydroalcoholic extract (B)
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FoodChemLab
Extracted ion chromatogram (XIC) of the ions related to main quercetin glycosides. TOF MS/MS of [M-H]- ions related to compounds 18 (B), 19 (C), 20 (D), 21 (E), and 31 (F).
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FoodChemLab
PCA Biplot representing the relationship between investigated hempseed oils (variables) and their percentage content (observations) in non-phenolic constituents (no-Ph), simple phenols derivatives (Ph) and flavonoids (Fla). Observations are also plotted as histograms. A) Data acquired for D1 hempseed oils
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FoodChemLab
PCA Biplot representing the relationship between investigated hempseed oils (variables) and their percentage content (observations) in non-phenolic constituents (no-Ph), simple phenols derivatives (Ph) and flavonoids (Fla). Observations are also plotted as histograms. B) data acquired for D2 hempseed oils.
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FoodChemLab
PCA Correlation circle and Observations map from data acquired for D1 hemp oils
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FoodChemLab
PCA Correlation circle and Observations map from data acquired for D2 hemp oils
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FoodChemLab
F C LUniCampania
FoodChemLab