vitamini b grupe
DESCRIPTION
Vitamini B grupeTRANSCRIPT
![Page 1: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/1.jpg)
TIAMIN, VITAMIN B1
3 - (4 -amino - 2 - metil - 5 - pirimidinil) - metil - 5' - hidroksietil - 4' - metil - tiazolium hlorid
1.
2Cl-H
12
3
4
56
1'2'
3' 4'
5'N
S
CH3
CH2CH2OH
N
NH3C NH2
![Page 2: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/2.jpg)
Osobine:beo kristalan prašak ili bezbojni kristali, gorkog ukusa, rastvoran u vodi i etanolu
kiseli vodeni rastvori (pH 3-4) su stabilni u prisustvu kiseonika, termo- i fotostabilni
termolabilan vodeni rastvor iznad pH 5 neutralan vodeni rastvor stajanjem žuti
![Page 3: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/3.jpg)
1. H+
H2ON
N
H CH2OH
H3C NH2
+N
S
CH3
CH2CH2OH
degradacioni proizvodi
OH
Oksitiamin
1. cH+N
S
CH3
CH2CH2OH
N
NH3C
![Page 4: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/4.jpg)
CH3
CH2CH2OHN
N
N NH2H3C C
O
HSH
Tiol degradacioni proizvod
1. OH -
pH 9 H
HO
N
S
CH3
CH2CH2OH
![Page 5: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/5.jpg)
U H+ rast. dominira tiazol a u OH- i neutralnim tiol.
U vodi obe forme su u ravnoteži: prisutna 2 apsorpciona maksimuma na 232 nm i na 266 nm.
![Page 6: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/6.jpg)
UV spektar tiamin hidrohloridaUV spektar tiamin hidrohlorida
Maksimumi apsorpcije:
Metanol: 262 nm, 238 nm
0.1M HCl: 246 nm
0.1M NaOH: 232 nm
![Page 7: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/7.jpg)
IR spektar tiamin nitrataIR spektar tiamin nitrata
![Page 8: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/8.jpg)
Identifikacija: Ph.Eur.1. IR spektri2. Tiohromna reakcija: svetlo plava fluorescencija u butanolu UV max. 365nm. Dodatkom mineralnih kiselina gasi se fluorescencija. Reakcija je specifična za vitamin B1 tek ako se izvodi u priustvu NaHSO3 ne sme doći do fluoroscencije!
![Page 9: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/9.jpg)
K-heksacijanoferat(III)
(365nm)
1.pH 11OH -
N
N N
N
S
CH3
CH2CH2OH
H
H3C
zut
oksidacija
H3C
CH2CH2OH
CH3
N
SN
N
N
TIOHROMfluoresciraplavo u butanolu
H, t
![Page 10: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/10.jpg)
1. + HSO3- + N
S
CH3
CH2CH2OH
N
N NH2
CH2SO3H
H3Cslabokiseor-raB1
Nu- jaciod H2O
- X-
![Page 11: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/11.jpg)
Određivanje:
TNS kao slaba baza sa HClO4. u HCOOH / (CH3COO)2O. z.t.t. potenciometrijski
kao hidrohlorid titracija sa 0.1M NaOH; z.t.t. potenciometrijski.
![Page 12: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/12.jpg)
RIBOFLAVIN VITAMIN B2
7, 8 - dimetil - 10 - (1 - D - ribitil) - 2, 4 - (3H, 10H) - benzopteridindion
N
N
N
N O
O
H3C
H3C H
CH2
CH2OH 3
CH2OH
1
2
34
567
8
9 10
![Page 13: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/13.jpg)
Osobine:
Žut do oranž - žut kristalan prašak, R. u vodi samo pri dodatku elektrolita ili uree kao polarnih komponenti, sa bazama gradi soli.U H+ sredini termostabilan (može da se steriliše) i prema O2 Rastvori fotosenzitivni, posebno u prisustvu alkalija. Nestabilan u OH- sredini. Optički je aktivan (C*u ribitil ostatku)
![Page 14: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/14.jpg)
RastvaranjeRastvaranje
N
R
HN
N O
O
N(Na)
H
N
N O
O
N
NH
R
DIKATIONu c.H2SO4 na N5
![Page 15: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/15.jpg)
•Neutralan rastvor ima žućkasto-zelenu fluorescenciju koja je pH zavisna!- Gasi se dodatkom H+, OH- ili redukcionih sredstava (Identifikacija!)
UV apsorpcija sa λmax= 223, 267, 373 i 444 → žuta boja služi u identifikaciji i određivanju.
U H+ sredini u prisustvu redukcionih sredstava Zn (HCl) ili Na2S2O4 gubi se žuta boja – dihidroriboflavin.
![Page 16: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/16.jpg)
UV spektar riboflavinaUV spektar riboflavina
![Page 17: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/17.jpg)
![Page 18: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/18.jpg)
Fotosenzitivan na povišenoj temperaturi - tip fd.p. zavisi od pH i prisustva kiseonika
![Page 19: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/19.jpg)
H
H3C
H3C N
N
N
N O
O
H
1.O2 H+ ili
neutralanrastvor
O2
cvrstneutralanrastvor
H
H3C
H3CN
N O
O
N
N
CH3 Hleukoriboflavinleukolumihrom
hv
zutlumihrom
oranzlumiflavin
TT 330oC TT 300oC
FOTOLITOCKI PROIZVODI RIBOFLAVINA
![Page 20: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/20.jpg)
Identifikacija i određivanje: Ph.Eur.
1. [α]D20 = -115 -135 (u baznim rastvorima).
ili u prisustvu boraksa kada o.a. jako raste ali je (+)!2. IR spektri 3. Gašenje žuto-zelene fluorescencije vodenog rastvora dodatkom min. kiseline ili baze.
Određivanje: spektrofotometrija, bazni rastvor λmax = 444 nm (Ph. Eur.) Izvodi se zaštićeno od svetlosti.
![Page 21: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/21.jpg)
Test čistoćeTest čistoće
Ispitivanje na lumiflavin TLC metodom ili
testom rastvaranja u hloroformu oslobođenim od etanola
fotod. proizvod rastvorljiv, riboflavin ne.
![Page 22: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/22.jpg)
PIRIDOKSIN VITAMIN B6
![Page 23: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/23.jpg)
Osobine:
u formi baze - bezbojni kristali rastvorni u organskim rastvaračima. T. T. = 160°C.
Hidrohlorid – bezbojan, kiselog ukusa, T. T. = 205°C ili 212°C, hidrosolubilan.
Vitamin B6 – amfoteran (pirid. N – bazan)
(fenol – kiseo)
![Page 24: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/24.jpg)
UV apsorpcija je pH zavisna
pH< 7
290 i 232 nm
N CH3
OH
CH2OH
HOH2C
H
+ H+ - H+
![Page 25: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/25.jpg)
pH > 7
245 i 309 nm
N CH3
O-
CH2OH
HOH2C
pH neutralno
253 i 324 nm
+ H+ - H+
HN CH3
O-
CH2OH
HOH2C
![Page 26: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/26.jpg)
OsobineOsobine
Stabilan je na vazduhu. Fotosenzibilan u alkalnim i neutralnim rastvorima.
Rastvori u mineralnim kiselinama su termostabilni i mogu biti autoklavirani na 120°C, 30 minuta, dok neutralni rastvori podležu polimerizaciji i oksidaciji
![Page 27: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/27.jpg)
Za analitiku važne:
1. OH grupa (fenolna – azafenol)2. N – bazan – piridinski3. α – pikolin (CH3 grupa kisela)4. bifunkcionalna parcijalna struktura fenola i susednih hidroksimetil grupa.5. pozicija 6 koja je sub. elektrofilnog napada (ES)
![Page 28: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/28.jpg)
Identifikacija po Ph.Eur.
1.UV spektar : 0.1M HCl. λmax 288-296 nm,
- u fosfatnom puferu dva λmax 248-256nm i 320-327nm
IR spektri (fenolna grupa) TLC metode-detekcija mrlja sa Gibbs-ovim
regensom
![Page 29: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/29.jpg)
UV spektar piridoksinaUV spektar piridoksina
0.1M HCl. λmax 288-296 nm,
- u fosfatnom puferu dva λmax
248-256nm i 320-327nm
U 0.1M NaOH takođe dva aps.
Max. 309 i 244nm
![Page 30: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/30.jpg)
IR spektar piridoksinaIR spektar piridoksina
![Page 31: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/31.jpg)
Ostale metode identifikacijeOstale metode identifikacije
Fenolna funkcionalna grupa: -Gibbs-ov reagens za VIS i TLC detekciju-FeCl3 - ljubičasta boja kompleksa i
-kuplovanje sa diazonijum solima R-ja alkilovanja sa CH3J Fluorescentni metod
![Page 32: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/32.jpg)
2,6-dihlorhinonhlorimid
Cl
Cl
ON
Cl
N CH3
O-
CH2OH
HOH2C
H-Cl-
- H+
O N N CH3
O-
CH2OHHOH2C
Cl
Cl
Indofenol plave bojemax 620 nm
![Page 33: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/33.jpg)
gde je fenol blokiran i reakcija sa Gibbs-ovim reagensom izostaje.Dodatkom H3BO3 raste specifičnost reakcije.
+ H3BO3
N CH3
O-
CH2OH
HOH2C
H
O
O
BOH
OH
H
N CH3
HOH2C-
Helat Bilidimerni helat B
![Page 34: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/34.jpg)
kuplovanje N CH3
CH2OH
HOH2C OH
R
N N
Cl-- HCl
N CH3
CH2OH
HOH2C OH
Ar N N
Azo bojazuto - narandzasta
![Page 35: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/35.jpg)
1. N CH3
CH2OH
HOH2C
CH3
OCH3
+ 2CH3J
OH-
CH2-
CH3
OCH3
N
CH2OH
HOH2C
CNO
H
CH3
CH3
H2O
ALDOLNAKONDENZACIJA
Reakcija sa CH3J
![Page 36: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/36.jpg)
CH2OH
HOH2C
N
CH3
OCH3
NCH3
CH3
CIANIN ( VIS APSORPCIJA )
![Page 37: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/37.jpg)
Fluorescentni metod
KMnO4
oksidacija
N CH3
OH
COOH
HOOC
N CH3
OH
CH2OH
HOH2C
N CH3
OHC
C
![Page 38: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/38.jpg)
N CH3
OHC
C
FLUORESCEINjaka fluorescencija
Određivanje: titracija u nevodenoj sredini sa HClO4 / HgAc2O z.t.t. potenciometrijski
![Page 39: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/39.jpg)
FOLNA KISELINA
CO
N
N CH2N
N
OH
H
H2N
NH NH CH
COOH
CH2
COOH
2
2 - amino - 3, 4 - dihidro - 4 - oxo - 6 - pteridinil metil
4 - amino - benzoil L - glutaminska kiselina
N - 4 [ 2 - amino - 3, 4 - dihidro - 4 - oxo - 6 - pteridinil metil amino] benzoil
- L - glutaminska kiselina
1.
![Page 40: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/40.jpg)
Osobine: žut prašak, nerastvoran u vodi i organskim rastvaračima, soli rastvorljive u vodi, rastv. u alkalnim hidroksidima, karbonatnim rastvorima i mineralnim kiselinama.
Spektralne osobine:
U baz. rast. tri aps. max. λmax = 256 nm, 283 nm (pteridin) i 365 nm (PAB).(Ph. Eur.)U kiselim rastvorima λmax = 298 nm
![Page 41: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/41.jpg)
Identifikacija: Ph.Eur.
1.) specifična optička rotacija u 0.1M NaOH je +18 do +22° 2.) HPLC metod iz određivanja (tR)
3.) TLC metod. Detekcija mrlja na 365nm UV denzitometrijski.
![Page 42: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/42.jpg)
Ostale identifikacije:Ostale identifikacije:
1. Cu(II)
alkalni rastvor
N
N
N
N
Cu
N
N
O
N
N
O
H2N
R
R
NH2
OXINAT - komplex
pahuljast zuckasto zeleni precipitat
![Page 43: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/43.jpg)
N
N
O
H
H2N N
N CH2 NH R+Zn
HCl
mucka i filtrira
N
N
O
H
H2N N
N CH3
RH2N
diazotacija i kuplovanje
filtratmetil pteridin
kvantitativna reakcija
3.
R= CO NH CH COOH(CH2)2
COOH
![Page 44: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/44.jpg)
4.
N
N
O
H
H2N N
N R
alkalni rastvor folne kiseline
KMnO4ili hO2
N
N
O
H
H2N N
N COOH
Violetboja - zelen (Mn (VI))fluorescencija
![Page 45: Vitamini B grupe](https://reader033.vdocuments.mx/reader033/viewer/2022061420/5695d4a11a28ab9b02a22b7a/html5/thumbnails/45.jpg)
Određivanje:
HPLC po Ph.Eur. spektrofotometrijski Za sve vitamine hromatografske metode
(TLC, HPLC, GH)