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підручники. біохімія / Uchebnik_po_Biokhimii_E_S_Severin

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TaK )!(e, KaK H rnIOKOJa, CYIIIecTByeT B IIHKJTH'lecKotf <PopMe, o6pa3y5t a- 11 P-aHoMepbt (pttc.

B. PEAKQIUI MOHOCAXAPlI,IJ,OB

ITpHCYTCTBHe rH,11,pOKCHJihHhIX, aJih,ll,erM,11,HhIX H KeTOHHbIX rpyrrrr TT03BOJI5leT MOHocaxapH)laM BCTYnaTh B peaKIIHH, xapaKTepHbte ,ll,JT5l CITHPTOB, aJibnertt,11,0B HJIH KeTOHOB. 3TH peaKIIHH JlOBOJibHO MHOfO'lHcneHHhI.B naHHOM paJnene 6y,11,yr orrttcaHhI JIHlllb HeKOTOpbie H3 HHX, rrpH'leMB OCHOBHOM

HMeIOIUHe HaH60JThWee 6HOJIOfWieCKOe 3Ha'leHHe.

B 3TOM pa3,11,ene OCHOBHhie peaKUHH MOHOCaxapM,11,0B paccMoTpeHhI Ha rrpHMepe D-rnIOK03hI (pHC. 7-5), xorn Ha)lO HMeTb B BH,11,y, 'ITOB MeTa60JIH3Me yrneB0,11,0B rrpHHHMaIOT y'laCTHe H ,11,pyrHe MOHOcaxapH,11,bI, a TaK)!(e HX npOH3B0,11,Hhie.

MyrapoTaIJ,HH, HJIH auoMepU3au,uH - B3aHMO-

rrpeBpallleHHe aHOMepHbIX cj)opM MOHOCaxapHJlOB. a- H P-<PopMbI aHoMepoB HaXOJl51TC5l B pacrnope B cocT051HHH paBHOBeCH5l. ITpH nocTH)!(eHHH 3Toro paBHOBeCH5l npo11cxon11T MYTapornumi - pa3MhtKaHHe H 3aMbIKaHHe IIHpaHOBOfO KOJibUa H, coOTBeTCTBeHHO, H3MeHeHwe pacrroJIO)!(eHH5l H- H OH-rpynrr rrpH rrepBOM yrnepo,11,e Mottocaxapm:i:a.

06pa30BaHHe fJIHK031VJ,OB. fJIHK03H)lHaH CB513b HMeeT Ba)!(HOe 6HOJIOrWieCKOe 3Ha'leHHe, ITOTOMY 'lTO HMeHHO c IlOMOlllblO 3TOH CB513H OCYIIIeCTBJl5IeTC5l KOBaJTeHTHOe CB513bIBaHHe MOHOCaxapH)lOB B COCTaBe onttro- H rronttcaxapH,11,0B. ITpH 06pa30Batt1111 rnHK03H,11,HOH CB513H attoMepttaH 0 H-rpyrr11a onHoro MOHOCaxapH)la B3aHMO,ll,eticTByeT c 0 H-rpyrrnoti npy-

298

AilbA03bl

 

 

 

 

 

 

 

 

D-pl-1603a (Rib)

 

D-KCW103a (Xyl)

 

L-apa6l-'!H03a(Ara)

 

H

 

 

H

 

 

H

 

 

 

HO

 

 

HO

H

 

H~

 

 

lOOH OH-

OH

H

OH

H

H

OH

~

H

~H

~H

 

neHT03bl

 

 

 

 

 

 

D-rmoKo3a {Glc)

D-MaHH03a (Man)

D-ra11aKT03a (Gal)

HOCH2

 

 

HOCH2

 

 

HOCH2

 

 

 

HO~HH OH

 

HO~HH H

H~~H

OH

 

H

OH

 

 

 

OH

 

HO OH

 

 

 

 

reKC03bl

KeT03b1

 

 

 

D-pl-16y1103a (Rub)

 

CH20H

~OH

H-CI -OH

I

 

 

 

C=O

 

 

 

I

H H .

H

CH20H

H-C-OH

 

 

 

I

OH

OH

 

CH20H

 

 

D-cj:>pyKT03a (Fru)

CH20H

 

 

 

I

 

 

 

C=O

 

 

 

I

 

 

 

HO-C-H

 

 

OH

I

 

 

HOtff

H-C-OH

I

H H

HO

CH20H

H-C-OH

 

 

 

I

 

 

 

CH20H

H

H

 

,Qe30KCM3flbA03bl

~-,.Q930KCll1-D-p111603a (dRib)

L-cj:>pyKTo3a (Fuc)

HOlO-

HO~H HO

H

 

H60

~

H OH

CH3

OH

 

 

OH

H

OH

H

A'-'enmMposaHHb1eaMMHocaxapa

N-a1..1ern11-D-rrnoKo- N-a1..1ern11-D-ra11aKT03-

3aM111H (GlcNAc)

aM111 H (GalNAc)

H~OCH2

 

H~~OCH2

 

0

 

~H

H

OH

~H

H OH

HO

2

HO

H

2

H

HN-C-CH3

H

HN-C-CH3

 

II

 

 

II

 

 

 

 

 

 

0

0

KMCflble MOHOCaxapMAbl

 

N-a1..1ernnHe~paM111-

CaxapocnMpTbl

 

0-rillOKYPOHOBaH

L-l-1..QypoHoeaH

 

HOBaH KlllCilOTa

 

 

 

 

(NeuAc)

D-cop6111T

D-MaHHl-'IT

Kl-'ICilOTa

KlllCilOTa

 

 

 

 

 

 

 

 

(GlcUA)

(lduUA)

 

 

9CH20H

CH20H

CH20H

 

 

 

 

 

I

I

I

~:a8~"OH

~~"OH

 

 

HO-C-H

H-C-OH

HO-C-H

 

 

 

I

I

I

 

 

 

H

HO-C-H

HO-C-H

HO-C-H

 

 

 

 

 

7

I

I

H6H'H~

 

 

 

 

H-C-OH

H-C-OH

 

 

 

 

I

I

3

 

 

6

H-C-OH

H-C-OH

 

 

 

 

CH20H

CH20H

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H OH

H OH

 

 

HN-C-CH3

 

 

 

 

 

 

II

 

 

 

 

 

 

0

 

 

=>Mc. 7-1. BaJKHeiiiwMe MOHOCaxapMAbl.

299

P11c. 7-2. D- 11 L-1130Mepb1 rnt0K03bl.

H OH

H OH

a-D-rmoKoaa

~-D-rmoKoaa

P11c. 7-3. a- 11 ~-aH0Mepb1 D-rnlOK03bl.

OH H

a-D-ct>pyKToaa

~-D-<1>pyKT03a

P11c. 7-4. a- 111 ~-aHoMepbl D-lj>pyKT03bl.

300

7- 7).
7-6).

 

 

rmoKypOHOBBS'I

 

 

 

rnlOKOHOBBS'I

 

 

 

Copfanon

 

 

KlllCilOTa

 

 

 

 

KlllCilOTa

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

6C008

 

 

 

Q

 

 

 

 

 

 

ltr'H OH

 

 

 

H

 

H

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H

H

 

 

 

 

 

~H

 

 

 

 

~H

H 0

 

 

 

~H H CH20H

 

 

HO

 

 

 

 

HO

 

1

 

 

 

HO

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

OK111cneH111e

 

 

 

 

OK111cneH111e

 

 

 

 

80CCTBHOBileH111e

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

~:~~~MyrapOTa"""~

~:~,

 

 

 

 

 

 

 

 

 

H~

 

 

 

 

 

 

 

H6H6H

 

 

 

 

 

 

 

 

H

 

OH

 

 

 

 

 

 

 

 

H

OH

 

 

 

 

 

 

 

 

13-D-mioKo3a

 

 

 

 

 

 

 

a-D-mioKo3a

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

06pa3oeaH111e

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

rfll!IK03111,Qa

0

0

6

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

II

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

o-~;o~CH2

 

 

 

 

 

:~OCH2OH

 

 

 

 

 

 

 

a-

H H

0 H

 

 

 

 

 

 

 

 

 

 

 

 

 

OH

H

 

 

 

 

 

 

 

~H HO

 

 

 

 

 

 

 

 

HO

 

H

 

 

 

 

 

HO

2

OH

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H

 

 

 

 

 

 

 

 

 

H

OH

 

 

 

 

 

 

 

 

 

H

 

 

 

 

 

 

 

 

r1110K030-

D-<!>pyKTo3a

 

a-D-MaHH03a

a-MeTlllilrfllOK03111Il

 

 

6-cpoccpaT

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

PMC. 7-5.

Pe8Kl.IMM MOHOCaxap~OB.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

roro MOHocaxapuna 11m1 cnttprn. flptt noM npottcXO.IUIT OTll.l,eruieHtte MOJie.K)'JihlBO,IJ,hl H o6pa30BaHHe 0-rJIBK03H,IJ,HOtt CBH3tt. Bee JIHHettHhie OJittroMephI (KpOMe JJ,ttcaxapH,IJ,OB) llJUf IIOJlllMepbI COJJ,ep)l(aT MOHOMepHbie OCTaTKH, yqaCTBYJOll.l,lle B o6pa30BaHllll

,IJ,Byx fJlllK03llJJ,HblX CB513ett, KpOMe KOHUeBblX OCTaTKOB, o6pa3YJ01UllX TOJlbKO OJJ.HY fJillK03H,Il,HYJO CBH3h. HeK0Topb1e rnm<03H,IJ,Hhie ocrnTKH Moryr o6pa30BhIBaTh TPH rJIHK03llJJ,Hhie CBH3H, 'ITOxapaKTeptto JJ,JI5I pa3BeTBJieHHhIX oJittro- H rroJittcaxapH,IJ,oB. OJIHro- H IIOJIHCaxapH,IJ,bI Moryr HMeTb KOHUeBOH OCTaTOK MOHocaxapH,IJ,a co coo6oJJ,Hotl: aHoMepttotl: OH-rpyrrrrotl:, He llCnOJih30BaHHOH rrpH o6pa30BaHttll rJIHK03H,IJ,- HOH CBH3H. B 3TOM cJiyt1ae nptt pa3MhIKaHIDi 11,HK1Ia B03M0)1(H0 06pa30Bam1e CB060JJ;HOH Kap6omrnhHOM

rpyrrnhI, crroco6HOH OKHCJIHTbCH. TaKtte OJIHro- H ITOJIHCaxapllJJ,bl o6Jia,IJ,aIOT BOCCTaHaBJIHBaIOW11Ml1 CBOMCTBaMH H I103TOMY Ha3bIBaIOTCH BOCCTaHaBJIHBaIOIUHMM, HJIM pe;:i;yuttpYJOll.l,MMH (pttc.

AttoMepHaH OH-rpyrrrra MOHOcaxapHJJ;a MO)l(eT B3attMOJJ.eti:crnoBaTh c NH2-rpyrrrrotl: ;:i;pymx coeJJ.H- HeHtttt, 1uo rrpMBO,IJ,HT K 06pa30BaH11IO N-rnttK0- 3HJJ;HOti: CBH3ll. flo;:i;o6HaH CBH3b np11cyrcrnyeT B

HyKJieoTH,IJ,ax 11 rJIMKonpoTettHax (p11c.

3TepmlmKaum1. 3TO peaKUHH o6pa30BaHHH

3qrnpttoil CBH3tt Me)l(JJ;y OH-rpyrrrraMH MOHocaxapttJJ.OB tt paJJrnqHhIMtt KHCJioTaMtt. B Mern6oJIH3Me yrneBo,IJ,oB Ba)l(HyIO poJih ttrpaIOT <Poc<Po3- <PttphI - 3cPllPhl MOHOCaxapllJJ,OB ll <Poc<PopHOM KHCJIOThI. B Mern6oJitt3Me rJIIOK03hI oco6oe Mee-

301

A "~}~"

a(1,4)-rm1K0311AHaSI CBSl3b a(1,6)-rn11K0311AHaSI CBSl3b

 

 

 

1~CH20H ~CH20H

 

5

\

0

O

0

 

OH

 

 

~; OH

 

OH

 

 

 

 

 

 

 

 

 

 

 

n

H

H

 

 

 

 

 

 

 

 

 

 

 

2

 

 

 

 

3

 

 

P111c. 7-6. CTpoeHMe non111caxap111Aa. A. 06pa3osaH11e a-1,4- 111 a-1,6-rn11K0311AHblX cssi3eii. 6. CrpoeH11e n11Hei1Horo non11caxap11Aa: 1 - a-1,4-rnlilK0311AHbl8 CBR311 Me~y MOHOMepaM11; 2 - HBBOCCTaHaBnlilBBIOLl.llllii KOHBLI (H8803MO)J(H0 o6pa30BaHl18 CB050AHOii Kap50HlilnbHOii rpynnbl y aHOMBpHoro yrnepoAa); 3 - BOCCTaHasn11sa10LL1lllii KOHBLI (B03MO)J(H0 pa3MblKBHl18 l.llllKna c o5pa30BBHl18M CB050AHOii Kap60HlilnbHOii rpynnbl y BHOMBpHoro yrnepoAa).

~o~

~OH

~ non11nenr11AHai:i 1.1enb

2

0-mlilK0311AHBSI CBR3b

PMC. 7-7. 06pa30BaHMe 0- MN-rnMK03MAHblX CBSl3eM BrnMKOnpoTeMHax. 1 - N-rnl1K0311AHBSI CBR3b Me~y aMlllAHOii rpynnoii acnaparnHa 111 OH-rpynnoii MOHocaxap11Aa; 2 - 0-rnlilK0311AHBR cssi3b MB)l(J:JY OH-rpynnoii cep11Ha 111 OH-rpynnoii M0Hocaxap11Aa.

302

TO 3amfMaeT rn10Ko3o-6-¢occjJaT. 06pa30Bam1e rn10Ko3o-6-cjJoc¢arn npo11cxo)J,HT B xo)J,e AT<l>-3a- BHCHMOH peaKU,l1l1 np11 yqacTl1l1 ¢epMeHTOB, OTHOC511Ul1XC51 K rpynne KHHa3. AT<t> B ,ri:attttotl. peaKutt11 BhICTynaeT KaK )J,OHOP cjJocQ:JaTHOH rpyrrnhl. <t>oc¢03¢11phl MOHOCaxapl1)J,OB MOryr o6pa30BblBaThC51 l1 6e3 l1CnOJih30BaHl151 AT<l>. Hanp11Mep, fJIIOK030-1-¢oc¢aT 06pa3yeTC5I 113 rJll1KOreHa npH yqacT1111 H 3P04<1>11311onorw1ecKoe 3Haqett11e Q:Joc- ¢03¢11poB MOHOCaxapl1)J,OB 3aKJJIOqaeTC51 B TOM' qTo 0Hl1 npe)J,CTaBJI51lOT co6otl. MeTa60JI11qeCKl1 aKTHBHhie CTPYKTYPhI. PeaKU,HJI Q:JoccjJoptt.n11poBatt11H MOHOCaxapH)J,OB Ba)[(Ha )J,Jl51 MeTa60Jil13Ma ewe l1 nOTOMy, qTO KJieTOlJHaJI MeM6patta MaJIO npOHl1uaeMa )J,JIJI 3Tl1X coe)J,11Hett11tl., T.e. KJieTKa y)J,ep- )[(llBaeT MOHOCaxapl1)J,hl 6Jiaro)J,ap51 TOMy, qTo 0Hl1 HaXO,!I51TC51 B ¢oc¢opHJIHpOBaHHOH ¢opMe.

0KUCJieHHe H BOCCTRHOBJieHHe. np11 OKl1CJieHHl1 KOttueBhIX rpyrrn rJIIOK03hI -CHO l1 -CH20H 06pa3y10TcJI 3 pa3JIMqHhIX npOH3BO)J,HhIX. Tlp11 OKHCJieHl1M rpyrrnhI -CHO 06pa3yeTC5I rJIIOKOHOBa51 KHCJIOTa. EcJIH 0K11cnett1110 no)J,BepraeTCJI KOHueBaJI

rpyrrrra -CH20H, 06pa3yeTC5I rJIIOKYPOHOBa51 KHCJIOTa. A ecn11 OKHCAAIOTCJI o6e KottueBhie rpynnhI, TO 06pa3yeTCH caxapttaJI KHCJIOTa, co)J,ep)[(aIUaH 2 Kap6oKCHJihHhie rpyrrrrhr. BoccrnttoBJiett11e nepBoro yrnepo)J,a npttBO)J,l1T K o6pa30BaH1110 caxapocn11prn - cop611ToJia.

B. OJUffOCAXAPM,11,hl

OnmocaxapH)J,hI co)J,ep)l((lT ttecKOJihKO (OT )J,Byx )J,O

)J,eC51Tl1) OCTaTKOB MOHOcaxapl1)J,OB,

coe)J,l1HeHHblX

rJIHK03H)J,HOM CB513bl0. Ll,11caxapH)J,bl -

HaH60Jiee pac-

npOCTPaHeHHhie OJIHTOMepHhie yrneBO)J,hl, BCTpeqaIOIUl1eC51 B CB06o)J,HOH Q:JopMe, T.e. He CB513aHHOM c )J,pyrHMH COe)J,HHeHH51MH. flo XHMHqeCKOH npMpO)J,e )J,11caxaptt)J,hI npe)J,CTaBJIHIOT co6otl. rn11K03H)J,hI, KO-

TOphie CO)J,ep)[(aT 2 MOHOCaxaptt)J,a, COe)J,l1HeHHbie rJIHK03H)J,HOH CB513hl0 B a- l1Jll1 ~-KOHcPHrypau11H.

B JTHIUe CO)J,ep)[(aTC51 B OCHOBHOM TaKHe )J,HCaxapH- )J,hl, KaK caxap03a, JiaKT03a l1 MaJihT03a (p11c. 7-8).

Caxap03a - )J,l1caxapH)J,, cocT051IUHH 113 a-D-rmo- K03hl l1 ~-0-Q:JpyKT03hI, coezurneHHhIX a,~-1,2-rnl1-

K03H)J,HOH CB513hl0. B caxap03e o6e attoMepttbie OH-rpyrrnhI ocrnTKOB rJIIOK03hI H Q:JpyKT03hI yqaCTBYIOT B o6pa30BaHHH rnttK03MHoi1 CB513l1. CJie- )J,OBaTeJihHO, caxap03a He OTHOCMTC51 K BOCCTaHaBJIMBalOIUMM caxapaM. Caxap03a - pacTBopHMhii1 )J,11caxapM co CJJa)J,KHM BKYCOM. l1cToqHHKOM caxapo3hI CJIY)[(aT pacTeHH51, oco6etttto caxapHM cBeK.lla,

caxapHbIH TPOCTHl1K. nocJie)J,Hee o6b51CH51eT B03Hl1KHOBeH11e rp11B11aJihHOro Ha3BaHtt51 caxapo3hI - «rpo-

CTHHKOBhii1 caxap».

JlaKT03a - MOJIOlfHbIH caxap; Ba)[(HeHlllHH )J,M- caxaptt)J, MOJJOKa MJ1eKon11rn10w11x. B KopoBheM MoJIOKe CO)J,ep)[(HTC51 )J,0 5% JiaKT03hI, B )l(eHCKOM MOJlOKe - )J,O 8%. B naKT03e attoMeptta51 OH-rpynna nepBoro yrnepo)J,ttoro aToMa ocrnTKa D-ranaKT03hI CB513aHa ~-rJJl1K03H)J,HOH CB513hl0 c lfeTBepTbIM yrJiepO)J,HblM aTOMOM D-rnIOK03hI (~- l ,4-CB513h). TloCKOJJhKY aHOMepHblH aTOM yrnepo)J,a OCTaTKa r.JJIOK03bl He yqacTByeT B o6pa30BaHMl1 rJIHK03H)J,HOH CB513l1, CJie)J,OBaTeJihHO, JiaKT03a OTHOCl1TC51 K BOCCTaHaBJIHBalOIUHM caxapaM.

MaJibT03a nocTynaeT c npO)J,YKTaMl1, co)J,ep)l(a- IUHMl1 qacTl1qHO rtt)J,pOJil130BaHHhlH KpaxMaJI, HanpttMep, coJIO)J,, rr11Bo. ManhT03a TaK)l(e 06pa3yeTc51 np11 pacwenJieH1111 KpaxMana B Kmueqtt11Ke. MaJihT03a cocTOl1T 113 )J,Byx OCTaTKOB D-rnIOK03hI, CoemrneHHhlX a- J ,4-rJJMK0311)J,HOH CB513hl0.

II10MaJ1bT03a - npoMe)l(yroqtthIH npo)J,yKT, 06pa3y10w11tl.c51 rrp11 pacwenJJett1111 KpaxMana B Kl1weqtt11Ke. CocTOl1T 113 )J,Byx ocrnTKOB D-rnIOK03hI, HO COe)J,l1HeHbI 3TH MOHOcaxapH)J,bl a- l ,6-rn11K0- 3l1.LI,HOH CB513bl0.

f. IlOJUICAXAPM)lhl

CTpyKTYPHhie pa3JIHq1151 Me)[(.LI,y noJJ11caxap11)J,a- MH onpe)J,eAAIOTC51:

CTpOeHHeM MOHOCaxapl1)J,OB, COCTaBJI51101Ul1X uenh;

TMOOM rJil1K03l1)J,HbIX CB513eH, coe)J,MHJllOIUHX

MOHOMephI B uentt;

• JTOCJie)J,OBaTeJihHOCThlO OCTaTKOB MOHOcaxap11-

)J,OB B uen11.

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