Le Hihi Thieng vd Dtg T?p chl KHOA HOC & C 6 N 0 N O H E 93(05): 47-51
TONG HglP VA NGHIEN ClTU CAC PHlTC CHAT CUA GADOLINI, TECBl, DYSPROSI V6l L- TYROSIN
Le Huu Thieng , Hd Thj Tuyen Trucmg Dgi hgc Suphgm - DH Thdi Nguyen TOM TAT
Bai bao ndy thong bdo kit qud t6ng hgp vd nghien curu cdc phdc chat cua gadolini (Gd), tecbi (Tb), dysprosi (Dy) vdi L- Tyrosin. Cdc phuc ch^t cCia gadolini, tecbi, dysprosi vdi L- Tyrosin ty I? moi 1: 3 da dupc tdch ra d dgng rftn bing phucmg phdp dong kit tua. Bang cdc phuong phdp phan lich nguyen td, phdn tich nhi?t vd quang phi h6ng ngogi da xdc djnh dupc cic phuc chat cd thdnh phdn la Ln(Tyr)3.3HiO (Ln: Gd. Tb, Dy). Phiic rSn t6ng hgp dugc k^m bin nhi^t, moi phan tii L- tyrosin lien kit vdi Ln'* qua nguyen tir nito cua nhdm amin - NH2 vd qua nguyen tir oxi ciia nhdm cacboxyl - COO".
T(r khda: phuc chdt. nguyen 16 ddt hiem. gadolini. tecbi. dysprosi. aminoaxit, L- Tyrosin
MO DAU
Phuc chdt ciia nguyen td dat hiem (NTDH) vdi cdc aminoaxit giif vai trd quan trpng trong sinh hpc, dugc phdm, ndng nghiep vd Id vat lipu chien luge cho cdc ngdnh cdng nghe cao [5]. Mpt sd phuc chat ciia NTDH vdi aminoaxit da dugc quan tdm va nghien cdu [2,3]. Trong bdi bao nay chung tdi thdng bao ket qud nghien cdu phdc ran cua gadolini (Gd), tecbi(Tb), dysprosi(Dy) vdi L- Tyrosin (Tyr).
THUC NGHIEM Tdng hap cdc phuc chat.
Phijrc chat ciia gadolini, tecbi, dysprosi vdi L- Tyrosin theo ti le moi Ln^* : Tyr = 1 : 3 dugc tdng hpp theo tdi lieu [4], Hda tan L- tyrosin (3mmol) va LiOH.H20 (3mmol) trong nudc cdt 2 ldn va hdn hgp dung djch ndy dugc dun ndng tren hep each thiiy d 70''C trong thdi gian khodng 20 phiit. Sau dd them dung dich mudi LnCl3 (Immol) vao hdn hgp dung dich Tyr-LiOH.HjO va khudy hdn hgp dung dich tren hep khudy tir 0 nhipt dg 50*'C trong thdi gian khoang 15 phut. Phuc chdt rdn dugc Ipc njra bdng nudc cdt ndng vd lam khd trong binh hiit dm. Cac phuc chdt khong cd mau, tan trong dimetyl sunphoxit (DMSO), (Ln^*: G d ' \ Tb^*, Dy^*).
Tel-0982 859002
Nghien ciru cau true eiia cdc phdc chat.
- Xdc djnh thdnh phan nguyen td ciia cdc phuc chdt: Ham lugng (%) ciia Gd, Tb, Dy trong phuc chat dugc xdc dinh bang each nung mdt lugng xac dinh phuc chat d nhiet dp 900 °C trong thdi gian 2 gid, d nhiet dp ndy phuc chat bi phan huy va chuyen ve dang oxit kim loai tuong ung LnjOj, hda tan oxit nay trong dung dich HCI IN rdi chudn do ion Ln^*
bang dung djch DTPA lO'^M, chi thi asenazo (III) 0,1%, dem pH =4,2.
- Ham lugng (%) cacbon, nito trong phuc chat dugc phan tich tren may phan tich nguyen td Analytik Jena AG, Customer Service, Konrad - zuse - str. 1, 07745 Jena (Due).
- Nghien cuu phuc chat bang phuong phap phan tich nhiet: Gian do phan tich nhiet ciia cdc phuc chat Gd, Tb, Dy vdi L - tyrosin dugc ghi tren may phan tich nhiet DTG - 60H shimazu ciia Nhat. Tdc dp gia nhiet Id 5°C/phut trong mdi trudng khdng khi, khodng nhiet dp tir 30"C din 9 0 0 ^ .
- Nghien cuu phuc chat bang phuong phap quang phd hdng ngogi: Phd hdp thy hdng ngoai cua L - tyrosin vd cdc phuc chat dugc ghi tren may Mangna IR 760 Spectrometer ESP Nicinet cua My, trong vung tan sd tii 400 -5- 4000 cm"'. Cac mau dugc trpn diu, nghien nhd vd ep vien vdi KBr. Su qui ket cdc ddi hap thy trong phd hdng ngogi cua L- tyrosin vd phuc chat dua theo tdi lieu [4].
Le Hihi Thieng va Dtg Tgp chi KHOA HQC & C 6 N G N G H S 93(05): 47-51 KET QUA v A T H A O LUAN
Ket qua phan tich thdnh phan (%) cdc nguyen to (Ln, C, N) cua cdc phuc chSt.
Cdc so lipu phdn tich thdnh phan phuc rdn dugc trinh bay trong bdng I.
Ket qud phan tich thdnh phan (%) cdc NTDH.
cacbon, nito gida li thuyet vd thyc nghiem ciia cdc phuc chat khdc nhau khdng nhilu.
Dieu dd cho thay cdng thuc gid thiet ciia cdc phuc chat Id tuong doi phii hgp. Rieng hdm lugng (so phan tu) nudc xdc djnh bdng thyc nghipm theo phuong phdp phan tich nhipt.
Ket qua phan tich gian 6h nhipt ciia cdc phuc chat.
Ket qua phan tich gian do nhipt ciia cdc phuc chat dugc trinh bay d hinh 1, hinh 2 vd bdng 2.
Hinh 1. Gidn do phdn lich nhipt cua phuc chJt Gd(TyrU3H20
Bang L Kit qud phdn tich thdnh phdn (%) cdc nguyen id (Ln, C, N) cita cdc phuc chdt
Cong thih; gia thiet
GdCTyr),.3H20 Tb(Tyr)!.3H,0 Dy(Tyr)j.3H20
LT 20,83 21,01 21,38
Ln TN 20,36 20,25 20,67
C L T 42,96 42,86 42,66
42,25 42,09 41,82
N L T 5,57 5,55 5.53
TN 5 0 2 5.18 5,04
(Ln: Gd. Tb, Dy; LT: li thuyet; TN: lh\rcnghi4m)
Bang 2. Kel qud phdn tich gidn do nhi^l cua cdc phuc chdi Phirc chat
Gd(Tyr)j.3H20
Tb(Tyr),.3H20
Dy(TyrJ, 3H,0
Hi^u trng thu
t"
(pic) 88,53
86,60
82,16 Dg gi&i
nhi^t n Ithoi liiViiE(%) LT 7,160
7,143
7,110 TN 7,SI4
6,889
6,170 Hifu t"
(pic)
266,76 416,50
268,32 432,04
261,12
-
442,48
irng t6a nhift D$ giam ithoi
lii?-ng (%) LT TN
20,460 38,895
21,297 39,997
23,215
-
41,515
cau dodn tir tdch ra
3H}0
3H2O
3H}0
Dtr dodn sdn phdm cu6i
-
Gdid
TbiOs
.
Dy,Oi (-) Khdng xdc dinh : LT: ll thuyet; TN; thuc nghiem
Le Hftu Thiing va Dtg Tgp chi KHOA HOC & C O N G N G H $ 93(05): 4 7 - 5 1
Hinh 2. Gidn do phdn lich nhiet cua phirc chdt Tb(Tyr)}.3H20
Quan sdt gidn d o phan tich nhipt ciia cdc p h d c chat (bdng 2, hinh 1,2 ) chiing tdi nhgn thay:
Gian do phan tich nhiet ciia c a c p h u c ch4t cd dgng gidng nhau, chiing td c h u n g cd cau triic t u o n g t y nhau.
Tren gian do phan tich nhiet cua cd 3 p h u c deu cd mpt hieu u n g thu nhiet va hai hieu umg toa nhiet Hieu d n g thu nhiet nam trong khoang nhiet dp t u 82,16 - 88,53*'C (thupc khoang nhiet dp m a t n u d c ket tinh ciia cac hgp chat) [1]. Hieu u n g tda nhiet t h u nhat nam trong khoang nhiet d o t u 261,22 266,76'''C. Cdn hieu u n g tda nhiet thu 2 nam trong khoang nhiet dp t d 4 1 6 , 5 0 - 442,48°C.
Q u a tinh toan dp giam khdi l u g n g tren d u d n g T G cua cac gian d o phan tich nhiet, d hieu ling thu nhiet cd ~ 3 phan t u n u d c ket tinh trong mdi p h u c chat tdch ra. C a c hieu ung tda nhiet u n g vdi q u a trinh chay va phan huy tuan t y cac thdnh phan con lgi cua moi p h d c chat.
(3 nhiet dp cao h o n nhiet dp cua hieu d n g toa nhiet t h u hai ddi vdi mdi p h u c chat thi dp gidm khdi l u g n g c u a c h u n g khong dang ke, chiing tdi cho rdng s u phan huy cac p h d c chat
dd xdy ra hoan toan va d y dodn san phdm cudi cung Id cdc oxit ddt hiem t u o n g ung Ln203 [5]. Nhiet dp phan huy cdc p h u c chdt khdng cao lam nen c h u n g tdi cho rdng cac phuc chat tdng hgp d u g c Id kem ben nhipt.
K i t q u a nghi€n c u u phd hdng ngoai cua cac phuc chat.
Ket qud nghien cdu pho hong ngoai ciia cac phuc chdt dugc trinh bdy d hinh 3 , 4 vd bang 3.
Hinh 3, Pho hdp thu hong ngogi ciia L- Tyr
''\\
Hinh 4. Pho hap thu hdng ngogi cija phirc chdt Dy(Tyr),.3H,0
Bang 3. Cere tan so hdp thu dgc trung (cm') cira L - tyrosin va cdc phirc chdt
Hop chat . ,coo- , ,coo-
AK.:
L - t y r o s i n Gd(Tyr)3.3H20 Tb(Tyr},.3HjO Dy (Tyr)3.3HiO
3136,34 3480,24 3223,91 3480,24 3216,79 3440,30 3218,50
1596,35 1450,40 1586,71 1414,61 1581,34 1413,04 1579,00 1412,11
145,95 172,10 168,30 166,89 f-) Khdng xdc dinh
Le H&u Thiing vd Dtg Tgp chl KHOA HQC & C 6 N G N G H $ 93(05): 47-51 Trong phd hong ngogi ciia L - tyrosin ddi hap
thy d tan so 3136,34 cm"' quy cho dao dpng hda trj ciia nhdm N H , \ Ddi hap thy d 1596,35 cm"' vd 1450,40 cm"' ddc trung cho dao dpng hda iri bai doi xung vd dao dpng hda trj doi xiing ciia nhdm COO".
Chimg loi nhgn thay pho hap thg hong ngogi ciia cac phdc chat deu khdc vdi pho ciia phoi tu ty do vl hinh dgng cung nhu vj Iri ciia cdc ddi hap thy. Dilu ndy cho biet sy tgo phuc dd xdy ra gida cac ion Gd'', Tb'*, Dy"" vdi L - tyrosin.
So sdnh pho hong ngogi ciia phuc chat vd pho hong ngogi ciia L - tyrosin d trgng thdi ty do (hinh 3) thay ddi hap thy d 1596 cm"' d^c trung cho dao dpng hda Irj bat doi xung (^^. ) cua nhdm COO" tren pho ciia L - tyrosin ty do dich chuyin vl vimg tan so thap hon (1586,71 cm"' - 1579,00 cm''), ddi hap thy d 1450,40 cm'' dac trung cho dao dpng hda trj ddi xung (f* ) ciia nhdm COO"
cung djch chuyen ve viing tan sd thdp hon (1414,61cm"' -^ 1412,11 cm"') tren pho ciia cdc phdc chdt. Dilu ndy chung td nhdm cacboxyl ciia L - tyrosin da lien ket vdi ion Ln^*. Sy chenh lech tan sd dao dpng hda tri bat ddi xung vd ddi xdng cua nhdm COO"
(Av^°f ) ciia phiic chdt khdc vdi ciia L - tyrosin ty do, chdng td L - tyrosin da lien ket vdi Ln"'* qua nguyen tu oxi ciia nhdm cacboxyl. Ddi dao dgng hda trj (w ' ) cCia nhdm NH3* tren phd cua L - tyrosin (3136,34 cm"') dich chuyen ien viing tan sd cao hon ( 3216,79 cm"' - 3223,91 cm"') tren pho ciia phuc chdt, chiing td L - tyrosin cung dd lien kit vdi Ln^* qua nguyen td nito ciia nhdm amin. Ngodi ra tren pho ciia cdc phdc chat cdn xudt hipn ddi hdp thy ddc trung cho dao
dpng hda trj ciia nhdm OH" ciia nudc (3440,30 cm"' ^ 3480,24 cm"'). Dieu ndy chdng td trong thdnh phan ciia cdc phuc Ln * cd chda nudc vd hodn todn phii hgp vdi kit qud nghien cdu phdc chat bdng phuong phap phan tich nhipt d tren.
KET LUAN
1. Da tong hgp dugc cdc phuc chat ciia Gd, Tb, Dy vdi L - tyrosin.
2. Bdng Ciic phuong phdp: phdn tich nguyen to, phdn tich nhiet vd quang pho hong ngogi cho thay:
- Cdc phiic rdn cd thdnh phan Ln(Tyr)3.3H20.
- Moi phdn tu- L - tyrosin chiim 2 vi tri ph6i tri trong phuc chat, lien kit vdi ion Ln^* qua nguyen tu nito cua nhdm amin -NH2 va qua nguyen tir oxi ciia nhdm cacboxyl -COO".
T A I LIEU THAM K H A O [1]. L6 Chi Kien (2007), Hoa hgc phirc chdi. Nxb Gido dye, Hd N^l.
[2]. Le Hihi Thiing, Nguyen VSn Dodn (2008),
" Tdng hgp vd nghien cuu tinh chdt phirc da nhan ciia lantan vdi axit L- glutamic". Tgp chl phdn llch Hod. Ly vd Sinh hgc. T- 13, sd 1, Uang 87-90.
[3]. Le Httu Thiing, Chu Thj Phuong HSng (2008), "Tdng hpp, nghien cuu phuc chat ciia prazeodim vd neodim vdi L- histidin". Tgp chi khoa hgc vd cdng ngh4 Dgi hgc Thdi Nguyen, s6 4(48), Uang 88-91.
[4]. Haoxu, Liang Chen (2003), "Study on the complex site of L - tyrosin with rare - earth element Eu^*", Spectrochim Ada Part 59, PP 657 - 662.
[5]. Moamen S.Refat, Sabiy A.EI-Korashy, Ahmed S.Ahmed (2008),"Preparation, structural characterization and biological evaluation of L - tyrosinate metal ion complex", Journal of Molecular S/ruc/ure 881, PP 28-45.
Le Hftu Thiing vd Dig Tap chl KHOA HOC & CONG N G H $
S Y N T H E S I S , S T U D Y O N T H E C O M P L E X E S O F
G A D O L I N I U M , T E R B I U M , D Y S P R O S I U M W I T H L _ T Y R O S I N E
Le Huu Thieng , Ha Thi Tuyen College of Education - TNU This paper reported the aggregate results and study the complex nature of gadolinium (Gd), terbium (Tb), Dysprosium (Dy) with L-tyrosine. The complex nature of gadolinium, terbium, dysprosium with L-tyrosine molar ratio 1: 3 was isolated in solid form by the precipitation method. By themethod of elemental analysis, thermal analysis and infrared spectroscopy have identifiedcomplexes is composed of Ln (Tyr)j.3H20 (Ln: Gd, Tb, Dy), Solid complexes areunstable thermal synthesis, L-Tyrosine per
molecule associated with Ln" * throughnitrogen atom of the amino group - NH2 and the oxygen atoms of the carboxyl group -COO'.
Key words: Complex, rare earth element, gadolinium, terbium, dysprosium . aminoacid, L- lyrosine.
Ngdy nhdn bdi;2/5/2012, ngdy phdn bien; 30/5/2012. ngdy duyel ddng: 12/6/2012
Tel: 0982 859002
