Nguyen Thu Hi^n vd Dig Tap chi KHOA HQC & CONG NGHE
106(06)'93-96NGHIEN c u t ; Sir TAO PHU'C DA P H 6 I TlT CUA MOT SO NGUYEN TO DAT HIEM NANG (Tb, Dy, Ho, Er) V 6 l L - TYROSIN VA AXETYL AXETON TRONG DUNG DICH BANG PHl/ONG PHAP CHUAN DO DO pH
Nguyen Thu Hien, Le Hu'u Thieng' Tru&ng Dai hgc Suphgm - Dll Thai Nguyen TOM TAT
Hdng so ben cua cdc phiic don, da phoi tu ciia mpt so nguyfin 16 ddt hifim nang (Tb, Dy, Ho, Er) voi L - tyrosin vd axetyl axeton da xdc djnh dupc bang phuong phdp chudn dp do pH d (30 ± 1 "C, 1 = 0,1) Cdc phirc chat vdi ti 1^ mol cua cdc cdu tu Id 1: 2 c6 d^ng LnTyr^* vd LnAcAc^"", Ln(AcAc)2^'' (Ln: Tb, Dy, Ho, Er). Sy tao phiic xay ra t6t trong khoang pH tir 6 dfin 8. Do bfin ciia cdc phiic ciiai tang tir Tb dfin Er.
Cdc phirc chat vdi ti I? 1:2,2 c6 dang LnAcAcTyr"", ti le 1 -4'2 c6 dang Ln(AcAc)2Tyr. Su tao phiic xay ra tot trong khoang pH tir 7 dfin 9. Op bfin ciia cac phiic chdt gidm lir Tb dfin Er.
Cdc phiic da phoi tii ben hon cdc phiic dan ph6i tir.
Tir kh6a: phue chdt, nguyen td ddt hiem, L - tyrosin. axetyl axeton
M C i D A U
Phirc chat ciia L - tyrosin vdi mdt so nguyen to dat hiem da dugc nhieu tac gia quan lam nghien ciru bdi sy da dang va irng dung ciia chung trong y dugc [6, 7]. Trong cae bai bao trudc [3, 4, 5] chiing toi thong bao ket qua long hgp phirc ran cua mgt so nguyen to dat hiem: Gd, Tb, Dy, Ho, Er, Lu vdi L - tyrosin va nghien ciru chiing bang cac phuang phap nhu phan lich nhiet, quang pho hdng ngoai, do do dan dien. Trong bai bao nay, chung toi trinh bay ket qua nghien ciiu sy tao phirc dan, da phoi tii ciia Tb, Dy, Ho, Er vdi L - Tyrosin (HTyr) va axetyl axeton (HAcAc) trong dung dich bang phuang phap chuan do do pH, THUC NGHIEM VA KET QUA Hoa chat va thiet bi
- Cac dung djch Tb^\ Dy^\ \\o^\ E?* duge chuSn bj tir cac oxit dat hiem tuang iing cCia hang Wako (Nhat Ban), do tinh khiet 99,99%.
- Cac dung dich L - Tyrosin, axetyl axeton tinh khiet hoa hgc duac xac dinh lai hang so phan li d dieu kien thi nghiem (30 ± I**C).
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- Dung dieh KOH diing de chuan do dugc ehuan bi lii ong ehuan.
Cac hoa chat khae trong qua trinh thi nghiem co do tinh khiet P.A.
- May do pH meter HM - 25R DKK - TOA (Nhat)
- May khuay tir co dieu chinh nhiet do.
Xac dinh hang so ben ciia phirc don phoi tir cua Tb^^ Dy^% Ho^\ Er^* vdi L - Tyrosin va axetyl axeton
Chuan do rieng re 50ml dung dich HTyr, HAcAc trong moi trudng axit khi khong va CO ion Ln^^ (Ln^^: Tb-'\ Dy' . H o ' \ Er'^) lay theo li Ie mol Ln-'^ HX = i :2 (HX: HTyr, HAcAc). Vdi eae nong dg Ln"'' la IO"^M bang dung dich KOH 5.IO"^Md30± l"C. Lye ion (I) trong cac tbi nghiem bang 0,1.
Kel qua chuan do (hinh I va 2) cho lhay trong khoang a = 1^2 (a la so duang Iugng KOH ket hgp vdi 1 mol HTyr hoac HAcAc) dudng cong chuan dg khi co ion dat hiem nam thap han xuong so vdi dudng cong chuan do dung dich HTyr hoac HAcAc ty do. Dieu nay chirng to da co sy tao phii'c, giai phong ion H"
lam giam pH ciia he. Sy tao phii'c xay ra tot trong khoang pH tu' 6^8.
93
Nguyen Thu Hien vd Dig Tap chi KHOA HQC & CONG NGHE 106(06): 9 3 - 9 6
Hinh 1. Dudng cong chudn do he HsTyr vd cdc he Ln^ N;Tyr = 1:2 bdng dung dich
KOH 5 10'Md30± l"C. 1^0.1 Trong do
1 - duang cong chudn do he HoTyr 2: dirdng cong chudn dp he Tb . H^Tyr 3 dudng cong chudn do he Dy . H2Tyr 4- dudng cong chudn dd he Ho^ : HfPyr 5. dudng cong chudn do h4 Er^ : H2Tyr
Vdi phdi lir la L - Tyrosin phdn img Igo phirc xdy ra.
L n ' ' + T y r ^—> L n T y r ' km LnTyr^* + T y r ^=± Ln(Tyr)2' ko;
* Vai phdi lir la axetyl axeton phdn img tao phue xdy ra:
Ln^* + AcAc" ^—> L n A c A c ' ' k|o L n A c A c ' ' " + A c A c " ^—> Ln(AcAc)2^ k2o Thiet lap cac p h u o n g trinh va sii' d u n g phan mem excel de tinh loan Sau khi xii li l h 6 n g ke, chiing loi thu d u g c cac ket qua n h u b a n g I va bang 2.
1100 p H 10.00 •
Hinh 2 h?Ln'
Trong do 1 2: dudng 3: dudng 4- dirdng 5. dudng
Biing 1.
Dudng cong chudn dp he HAcAc vd cac
•HAcAc= I 2 bdng dung dich KOH 5. Iff
\\l a30± l"C. 1 = 0.1
cong chudn dd he HAcAc cong chudn dp h? Tb' : HAcAc cong chudn dp he Dy' : HAcAc cong chudn dp hi Ho : HAcAc cong chudn dp he Er' . HAcAc C 'ac ghi iripK cua L - Tyrosin vd axetyl
axeton a 30 ± fc. I = 0,1 Ph6i t u
L - T \ r o s m A\et\ 1 .i\oton
p K , 2.25
p K i 8.96
pK»
9.36 (-) khdng xdc dink.
Ket q u a n a y phii h g p v d i ket q u a d tai lieu
[1,7],
Bang 2. Logant hdngsd ben cua Tb , Dy . Ho' , Er' vai L -~ Tyrosin vd axetyl axeton
a30± l"C. 1 = 0.1
Ln"
Lgkii Lgkio l.gl<20
Tb"
5.47 6.29 10.04
Dv"
5.61 6.40 10.53
Ho"
5.85 6 49 11.09
Er"
6.17
6.70
11.82
Nguyen Thu Hifin va Dig Tap chi KHOA HOC & CONG NGHE Ket qua d bang 2 c h o t h i y :
Hang sd ben eiia cac phirc c h i t eiia Tb^*, Dy^*, Ho^*, Er^" vdi L - Tyrosin va axetyl axeton tang dSn tir Tb"'* den Er'"^ hoan loan phu hgp quy luat.
Nghien cu-u su- t a o p h i r c d a p h o i tu- ctia Tb^*, D y ^ ^ H o ^ \ Er^* v d i L - T y r o s i n va axetyl a x e t o n
Chuan dg 50ml d u n g dich hon hgp H T j r . HAcAc Irong mdi I r u d n g axit khi khong va CO ion Ln'* ( L n ' ' : T b ^ \ D y ^ \ H o ' \ Er'") i i y theo cac li le mol L n ' ' : H A c A e : HTyr = 1:2:2 va 1:4:2 vdi n o n e d o Ln " la 10' M bang dung djch K O H 5.I0'-M d 30 ± I^C. Lye ion (I) trong eae thi nghi?m bang 0 , 1 . Kel qua ehuan dg eho thay trong khoang a = l - 2 (a la so d u a n g l u g n g K O H ket hgp vdi I mol HTyr hoac H A c A c ) d u d n g c o n g chuan do khi CO ion dat hiem nam thap han xuong so vdi dudng c o n g ehuan dp d u n g dich HTyr hoac HAcAe t y do. Di^u nay c h u n g to da co su tao phirc xay ra. S y lao p h u e xay ra tot trong khoang pH tir 7 - 9 .
* Vdi li le mol Ln^ : HAcAc : HTyr = 1 -2.2, phdn u-ng tgo phirc xdy ra nhir sau:
Ln* + Tyr" <—- LnTyr"* koi Ln'* + AcAc" *-—- LnAcAc^' k]o LnAcAc-*+Tyr" ^ = ^ LnAcAcTyr* k m ^ " ^ ' ^ ' LnTyr^* + A c A c " ^=^ LnAcAcTyr ' k|||'-""^="
Ap dung dinh luat bao loan nong d o ban dau va dinh luat bao toan dien tich, chung loi thu dugc he 4 p h u a n g trinh sau:
C,,,„, =:r(;|- + ^ + l) + *.,« + t„^^-" (1)
Q A . A C = yi-rr + 1 ) + ^lo^z + ''m^y^' (2) C.^=z + kf|,xz + k^^,yz + kQ^xyzl (3)
,h If ^ h x(—+ ) + v . — =
P-°)-(c„_„,+c„^,j-ft+^ (4)
Trong do:Kl, K2 la cac hdng so phan Ii ciia HTyr, KA la ' hang s6 phan li ciia H A c A c ; koi, kjo la hang so bSn ciia phiic chat giira Ln^* vdi HTyr va -
HAcAc; Kw la lich so ion ciia nudc. [Tyf] = x;
[ A c A c ] = y ; [Ln^*] = z; km'""'^''' = t; [H*] = h.
Diing phan mem Maple 13.0 de giai cac p h u a n g trinh lir (^I) - (4) vdi cac an so x, y, z, I; tir gia tri k| 11^" ""'' chiing toi tinh hang so ben long c g n g cCia phiic chat L n A c A c T y r ' theo e d n g thiic:
=koi kn LnTyr bay Igp 11 Igko, Ket qua d u g c trinh bay d bang 3 .
Bang 3. Logaril hdngsd ben cua cdc phirc LnAcAcTyr o30± l"C. 1 = 0,1
Ln"
IgPn,
Tb'*10 73
Dy"
10.51
Ho"
10.04 F.r'*
9.32
* Vol ti le mol Ln' : HAcAc : HTyr = phdn img Igo phik: xdy ra nhir sau.
Ln^'' + Tyr" <—- L n T y r ' ' koi Ln""" + AeAe" ' = ^ ' L n A c A c ^ * kio L n A c A c ^ * + A c A c " * ^ ^ Ln(AcAc)2" I LnAcAc^* + Tyr" *—- LnAcAcTyr*
LnTyr"* + A c A c " < = ^ L n A c A c T y r ' k| 1 Ln(AcAc)2*+ Tyr" ' — - Ln(AcAc)2Tyr
, , , , , A . A .
LnAcAcTyr* + A c A c - Ln(AcAc)2Tyr
Thiel lap cac phuong trinh va tinh hang so ben cua phiic t u a n g ty nhu phiic chat LnAcAcTyr*, chung toi thu dugc ket qua d bang 4.
Bang 4. Logaril hdng sd ben ciia cdc phirc chdt Ln(AcAc)2Tyr a 30 ± l"C. 1 = 0.1
Ln' Ho^* Er^*
21.82 21,69 Ket qua:
Ci bang 3 va bang 4 cho thay, hang so ben ciia cae phiie chat LnAcAcTyr* va Ln(AcAc)2Tyr giam dan lir T b den Er, dieu nay phii hop vdi quy luat doi vdi cae phiie da phoi lii.
Cac bang 2, 3, 4 cho lhay phiie da phoi l u ben hon cac phiic d a n phoi tir, dieu nay co the do
95
Nguyen Thu Hien vd Dig Tap chl KHOA HQC & CONG NGHE 1 0 6 ( 0 6 ) ' 9 3 - 9 6 phirc da ^h6i tir cd e i u triic phan l u doi xirng
va CO sy on djnh bdi c a c t n r d n g phoi lir \2\.
K E T L U A N
- Da xac dinh dirge h i n g so phan li ciia L - Tyrosin va axetyl axeton d 30 ± 1 C, I = 0 , 1 . - i);i x^c dinh dtrgc h i n g so ben ciia eae phirc dan phoi l u tao thanh giii'a T b " . Dy*'*, Ho ' , E r ' ' vdl L ~ Tyrosin va axetyl axeton theo li le s6 mol L n " : H T y r - 1:2 va L n " : H A c A c '- 1:2. C a c phirc chat co dang: LnTyr^', I n A c A c ' ' va Ln(AcAc)2*. S y lao phiic xay ra t6l irong k h o a n g pH l u 6 den 8, Do ben eiia cac phirc chat tang dan tir T b d£n Er.
- Da xac djnh d u g c hang so ben ciia cac phiic da phoi tli lao thanh giiia T b " , D y " , H o " , Er'* vdi L - Tyrosin va axetyl axeton theo li le so mol
L n " : H A c A c : H T y r = 1:2:2 L n " : H A c A c : H T y r = 1:4 2
- Su tao phirc xay ra t6t d pH tir 7 den 9, D o b6n cua cac phiic chat giam dan tii' T b den Er.
- Phirc chat da ph6i t d b6n h a n p h u e chat dem phoi ttr.
T A I L I $ U T H A M K H A O [l], Nguyin Trpng Bifiu, Tu VSn M|c (1978), Thudc thu huu ca. Nxb Khoa hpc vd KT thuat Ha Npi, Ir 55.
[2]. Uh Vifit Quy (1999), Phirc chdt trong hda hQc Nxb Khoa hpc \k KT thu^t Hd Npi, tr 291.
[3]. Le Htru Thifing, Hd Thj Tu^yfin (2012), "Tonghgp vd nghien cihi cdc phirc chat cua gadolini, tecbi, dysprosi vdi L - tyrosin", Tap chi Khoa hoc vd Cong nghv • Dpi hoc Thdi Nguyen. T93, S6 05, tr 47-51. _ [4], Le Hdu Thicng, Truong Thj Hudn (2012), "T6ng hgp, nghien ciiu phirc chat cua honmi, erbi v6i L - tyrosin". Tap chi I Ida HQC. T50(5B), tr 79-82.
[5]. Le HOu Thifing, Nguyen Trpng IJ> en, Nguyen Thi Hifiu (2013), "Nghien cim sy tao phiic ciia samary v6i L -tyrosin". Tap chl Hoa hoc. yjOrJA tr 336-339.
[6]. Haoxu, Liang Chen (2003). "Study on the complex site of L - tyrosine with rare earth element Eu"", Spectrochimica Ada Part .459. pp 657-662.
[7]. Moamen S.Refat, Sabry A. El - Korashy, Ahmed S.Ahmed (2008), "Preparation, Structural characterization and biological evaluation of L - tyrosinate metal ion complexes". Journal of Molecular Stnicture 881. pp 28-45
IS]. Shimadzu (1996), "HPLC aminoacid analysis system", Applicalion data book cl90- E 004. pp 05.
S U M M A R Y
S T U D Y O N F O R M A T I O N O F M I X E D L I G A N D C O M P L K X E S O F S O M E H E A V Y R A R E E A R T H E L E M E N T S ( T b , Dy, H o , E r ) W I T H L - T Y R O S I N E A N D A C E T Y L A C E T O N E IN F L U I D BY P O T E N T I O M E T R I C T I T R A T I O N IN A Q U E O U S S O L U T I O N
Nguyen Thu Hien, Le Huu Thieng' College of Education - 7-,V(/
The stability constant of the mixed ligand complexes and simple ligand complexes formed between Tb'*, Dy^*, H o " , E r " with L - Tyrosine and acetyl acetone u c r c determined by polentiometric titration in aqueous solution (30 ± l°C, 1 = 0,1).
The complexes in the molar proportion I: 2 have form of LnTyr' and L n A c A c ' ' , Ln(AcAc)2"*
(Ln' Tb, Dy, Ho, Er). The best formation of complexes occurs in the range of pH fi-om 6 to 8. The stability constant of complexes increases from Tb to Er.
The complexes in the molar proportion 1: 2: 2 proportion have form of LnAcAcTyr*, following 1:4:2 proportion have form of Ln( Ac Ac)2Tyr. The best formation of complexes occurs in the range of pM from 7 lo 9, The stability conslant of complexes decreases from Tb to Er.
The mixed ligand complexes turned out to be much stronger than the simple ligand complexes.
Key words: Complexes, rare earth elements, L - Tyrosine, acetyl acetone
Ngdy nhdn bdi 23/5/2013. Ngdy phdn biin. 20/7/2013, Ngdy duyel dang. 26/7/2013
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