TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).

2010

TNG HP PHC CHT A PHI T CA NGUYN T T HIM V TH NGHIM HOT TNH SINH HC N S SINH TRNG PHT TRIN CA CY U TNG
SYNTHESIS OF MULTI-LIGAND COMPLEX OF RARE EARTHS AND ITS APPLICATION TO THE BIOLOGICAL ACTIVITY ON THE GROWTH AND DEVELOPMENT OF THE SOYBEAN Phm Vn Hai
i hc Nng

Nguyn Tn L
Trng i hc S phm, i hc Nng
TM TT

Trong bi bo ny, trnh by phng php tng hp phc cht glutamat molypdat neodim v th nghim hot tnh sinh hc ca phc cht . Phc cht ny c tng hp t ion t him Nd3+ v axit glutamic vi Na2MoO4. Cc iu kin ti u ca qu trnh tng hp phc c xc nh thng qua php chun to phc vi cht chun DTPA v cht ch th Arsenazo (III). Cc yu t nh hng n hiu sut phn ng tng hp bao gm t l cc cht phn ng, thi gian, nhit , pH ca dung dch cng c xc nh. Thng qua cc phng php phn tch nhit v ph hng ngoi xc nh c cng thc ha hc ca phc cht a phi t ca nguyn t t him Nd vi axit glutamic v Na2MoO4. T phc cht tng hp, c ng dng kim tra hot tnh sinh hc ca chng thng qua qu trnh thm d s sinh trng v pht trin ca cy u tng. Vi phng php pha ch dung dch phc cht glutamat molypdat neodim cc nng thch hp ngm ht u v phun trn l cy u tng thu c kt qu rt tt, c th chiu cao, din tch l, trng lng ti v trng lng kh ca cy u tng giai on ra hoa u tng ln; rt ngn c thi gian ra hoa; lm tng cng quang hp, cng h hp ca cy; hm lng protit v lipit trong ht u tng. ABSTRAST In this paper, the neodymium glutamate molybdate complex compound has been synthesized and tested for its biological activity.The study on the production of a complex formation of the neodymium (III) with L-glutamic acid and sodium molybdate has been carried out. Optimal conditions of complex synthesis have been determined via reaction performance based on the DTPA complexometric titration method with Arsenazo (III) as an indicator. Besides, the influences of other factors such as molar ratio of Nd3+:H2Glu:MoO42-, the temperature, time and pH of the solution on the reaction performance have been surveyed. Based on the thermal analysis and infrared spectroscopy methods, the formula of the multiligands complex compound have been determined as Nd(HGlu)(MoO4).2H2O. Its biological activity has been further tested on the growth and development of the soybean. By using a suitable solution to soak the seeds and to spay on the leaves of soybean in an experiment conducted in Danang, the following experimental results are obtained: the height, assimilation surface, fresh and dry weight of the plant have increased; the flowering has been premature; there has been an increase in the content of total chlorophyll, the intensity of photosynthesis and respiration. In all, the productivity, both protein and lipid contents in the grains of the experimental soybean have increased in comparison with the controlled lot. 84

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1. M u Phc cht ca nguyn t t him vi mt s axit hu c c nghin cu v ng dng trong nhiu lnh vc khc nhau nh trong y hc, nng nghip, cng ngh sinh hc... Cc kt qu nghin cu khng nh phc cht ca nguyn t t him v mt s nguyn t vi lng vi cc axit hu c c hot tnh sinh hc [4], [6]. Trong bi bo ny, chng ti thng bo kt qu nghin cu tng hp phc rn glutamat molypdat neodim Nd(HGlu)(MoO4).2H2O v th nghim nh hng ca n n qu trnh sinh trng pht trin ca cy u tng (Glycine max L.). 2. Phn thc nghim Tin hnh thc nghim bng cch to kt ta Nd(OH)3 vi dung dch NH3 d t dung dch ban u Nd(NO3)3 c xc nh nng , ra kt ta nhiu ln bng nc ct lm sch NH3 c trong kt ta. Tnh ton lng dung dch axit L-glutamic v mui natri molypdat theo t l mol cn thit so vi Nd3+ ri cho vo cc thu tinh c cha kt ta. Sau mt thi gian nht nh, ly mu chun lng Nd3+ cn li sau phn ng bng DTPA, vi cht ch th Arsenazo(III), trong mi trng m pH = 4,2. T tnh c hiu sut ca phn ng. Cu trc ca phc tng hp c kho st bng phng php hng ngoi v phn tch nhit DTA. Hot tnh sinh hc ca phc cht c thm d bng cch kho st nh hng ca phc cht tng hp n mt s ch tiu sinh l sinh ha cng nh ch tiu sinh trng, pht trin, nng sut v phm cht ht ca cy u tng. Cc s liu phn tch, x l s liu c xc nh theo cc phng php nghin cu sinh l thc vt thng dng, m bo chnh xc v tin cy. 3. Kt qu v tho lun 3.1. Tng hp phc rn glutamat molypdat neodim Trn c s cc iu kin ti u ca phn ng to phc gia axit L-glutamic (H2Glu) v axit boric vi neodim nghin cu [2], chng ti tin hnh tng hp phc cht rn glutamat molypdat neodim (GMoN) nh sau: cho dung dch Nd(NO3)3 vo ng ly tm, tin hnh kt ta hidroxit neodim bng NH4OH vi mt lng hi tha kt ta ht Nd3+ bng cch nh t t dung dch amoniac v khuy bng a thy tinh to kt ta bng ( lng phn nc trong, c pH khong 9). Ra sch kt ta bng phng php gn kt hp ly tm cho n khi nc ra c pH 7. Chuyn ton b kt ta Nd(OH)3 mi sinh vo cc thy tinh cha sn lng chnh xc H2Glu v Na2MoO4, iu chnh pH ca dung dch hn hp v gi tr pH = 6,0. Nng nhit ln 600C v tin hnh khuy trn trn my khuy t c bp n nhit trong thi gian 2 gi. C hn hp phn ng 60 - 700C trn bp cch thy cho n khi xut hin vng trong sut trn b mt. ngui, kt ta s dn tch ra, lc ly kt ta, ra bng etanol tuyt i v lm kh. Phc glutamat molypdat neodim tng hp c l mt cht rn mu hng nht. 3.1.1. Nghin cu phc cht bng phng php quang ph hng ngoi Ph hp th hng ngoi ca axit H2Glu v phc glutamat molypdat neodim c
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TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).2010

ghi trn my Impact 410-Nicolet (M) trong vng 4000 400cm1. Kt qu c ch ra trn Hnh 1, Hnh 2 v Bng 1.
Bng 1. Cc tn s hp th chnh ca cc hp cht

Hp cht H2Glu GMoN

NH 2
3426,17

NH3

COO as

NH 2
1547,99

NH3

COO s

3060,35 2084,83 -

1644,64 1619,05

1512,67 -

1419,19 1414,75

Ph hp th hng ngoi ca phc cht khc vi ph ca axit L-glutamic t do v hnh dng cng nh v tr ca cc di hp th c trng. iu ny cho thy s to phc xy ra gia ion Nd3+ vi axit L-glutamic v molypdat. Trn ph hng ngoi ca phc glutamat molypdat neodim c s dch chuyn ln ti nhm NH3+ t 3060,35cm1 (trong ph ca axit L-glutamic) n 3426,17cm1 ng vi dao ng ho tr ca nhm NH2 bo ha, chng t c s phi tr gia Nd v NH2 gy ra s chuyn dch ny. Hn na, s mt i hon ton cc i hp th 2084,83cm1 ng vi dao ng ha tr nhm NH3+ (trong ph ca axit L-glutamic), ng thi xut hin vn hp th 1547,99cm1 ng vi dao ng bin dng ca nhm NH2 cng l mt bng chng ca s to phc xy ra. Cc di hp th 1644,64cm1 v 1419,19cm1 c trng cho dao ng ho tr bt i xng v i xng tng ng ca nhm COO trn ph ca axit L-glutamic t do dch chuyn v vng tn s thp hn (1619,05cm1 v 1414,75cm1) trn ph ca phc cht chng t nhm cacboxyl ca axit L-glutamic phi tr vi ion Nd3+. Cc di hp th cc tn s 929,18cm1; 852,20cm1; 760,41cm1 v 698,23cm1 c gn cho cc dao ng ca nhm Molypdat MoO4, trong di hp th 929,18cm1 ng vi dao ng ho tr ca lin kt Mo=O, cc di 852,2cm1 v 760,41cm1 ng vi dao ng ho tr bt i xng ca lin kt MoO v di hp th 698,23cm1 tng ng vi dao ng bin dng lin kt MoO.

Hnh 1. Ph hp th hng ngoi ca axit L-glutamic 86

TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).2010

Hnh 2. Ph hp th hng ngoi ca phc glutamat molypdat neodim

T cc kt qu nghin cu v phn tch nu trn c th thy phc cht a phi t ca Nd vi axit L-glutamic v molypdat thu c c thnh phn l Nd(HGlu)(MoO4). Trong , axit L-glutamic v molypdat lin kt vi ion Nd3+ qua cc nguyn t nit v oxi.
3+

3.1.2. Nghin cu phc cht bng phng php phn tch nhit Gin phn tch nhit ca phc glutamat molypdat neodim c ghi trn my Shimadzu TA50 (Nht Bn). Tc nng nhit l 100C trong 1 pht ngoi khng kh, khong nhit 30-7000C. Kt qu nghin cu c trnh by Hnh 3, Hnh 4.

Hnh 3. Gin DTA ca phc

Hnh 4. Gin TGA ca phc

Gin phn tch nhit ca phc GMoN cho thy trn ng cong DTA c mt hiu ng thu nhit 52,510C v mt hiu ng ta nhit 349,980C. Gin TGA ca phc ch ra rng qu trnh phn hy phc GMoN c th chia thnh 2 giai on. Giai on u tin hon tt ti 1000C ng vi vic gim 7,59% khi lng. Khi lng gim ny ph hp vi gi tr l thuyt ca 7,408% khi lng tng ng vi 2 phn t nc tch ra. Giai on th hai kt thc 7000C ng vi 11,069% khi lng gim xung
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TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).2010

khi nhit ln n 4250C v t 4250C n 7000C ghi nhn s mt i 7,184% khi lng. Giai on th hai ny tng ng vi s phn hy dn dn ca ion HGlu. Sau 2 giai on, khi lng cn li l 74,157% tng ng vi khi lng tng cng (74,068%) ca Nd2O3 , 4 C v MoO3 [5]. T cc kt qu thu c hai phng php phn tch trn y, ta c th d on cng thc ca phc cht tng hp t Nd3+, axit L-glutamic v natri molypdat l Nd(HGlu)(MoO4).2H2O. 3.2. Thm d hot tnh sinh hc ca phc glutamat molypdat neodim Vic thm d hot tnh sinh hc ca phc glutamat molypdat neodim ( GMoN ) Nd(HGlu)(MoO4).2H2O c tin hnh bng cch kho st nh hng ca phc n cc ch tiu sinh trng pht trin, sinh l sinh ha, nng sut v phm cht ca cy u tng, trng th nghim ti Nng. u tng l loi cy h u, giu hm lng protein, c trng lm thc n cho ngi v gia sc [1]. Trong cc nguyn t vi lng, molipden c kh nng tng cng c nh m ca vi khun nt sn, l thnh phn ca enzim kh nitrat, tham gia vo qu trnh tng hp protein, trao i hydrat cacbon, tng hp dip lc, cc vitamin v axit nucleic [3] Phc GMoN c s dng vi nng thch hp dng ngm ht trong 2 gi trc khi gieo v phun vo l cc giai on sinh trng khi cy c 3 l, 5 l, ra 80 hoa v kt thc ra hoa.
70 60 50 40 30 20 10 0 50 100 150 200

3.2.1. Xc nh nng x l Nng phc GMoN x l c xc nh thng qua t l ny mm ca ht u tng. Pha long dung dch phc GMoN vi cc nng 50 ppm, 100 ppm, 150 ppm, 200 ppm ngm ht trong thi gian 2 gi trc khi gieo vo a petri. Sau 24 gi gieo ht, chng ti thu c t l ny mm ng vi cc nng khc nhau c trnh by hnh 5. Da vo kt qu thu c, chng ti chn nng phc GMoN 100 ppm lm nng thch hp x l ngm ht v phun vo l trong sut qu trnh th nghim.

Hnh 5. nh hng nng phc GMoN n t l ny mm ca ht u tng.

3.2.2. nh hng ca phc GMoN n s sinh trng pht trin ca cy u tng D nh hng ca phc GMoN, chiu cao cy, din tch l, trng lng ti v trng lng kh ca cy u tng giai on ra hoa c s gia tng so vi i chng. Kt qu trnh by bng 2:
Bng 2. nh hng ca phc GMoN n cc ch tiu sinh trng ca cy u tng

Ch tiu theo di

i chng x m CV% 5,27 x m

Phc GMoN CV% % so vi C 139,62 71,91 1,70 6,31

Chiu cao thn (cm) 51,50 2,11

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TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).2010

Din tch l (dm2)

13,71 0,57

4,83 6,18 4,23

16,52 0,61 5,72 64,73 1,63 7,26 21,51 1,68 5,03

120,41 128,62 129,83

Trng lng ti (g) 50,33 1,44 Trng lng kh (g) 16,56 1,39

Theo di thi im ra hoa, chng ti nhn thy cy u tng c x l phc GMoN ra hoa sau khi gieo 50 ngy vi tng s hoa c t l 74,67 hoa; cy i chng ra hoa mun hn, thi im 53 ngy, s lng hoa t hn, vi tng s 61,63 hoa. 3.2.3. nh hng ca phc GMoN n mt s ch tiu sinh l sinh ha Theo di hot ng quang hp v hot ng h hp l ca cy u tng giai on 7 l, chng ti thu c kt qu trnh by bng 3.
Bng 3: nh hng ca phc GMoN n cc ch tiu sinh l sinh ha ca cy u tng

Ch tiu theo di

i chng x m CV% 3,72 4,23 3,18 x m

Phc GMoN CV% % so vi C 113,70 135,81 112,06 2,36 0,01 4,27 2,01 0,02 5,14 1,30 0,01 4,23

Hm lng dip lc tng 2,08 0,01 s (mg/g) Cng quang (mg/dm2/gi) Cng h 2 (mgCO2/dm /gi) hp 1,48 0,01 hp 1,16 0,03

Kt qu cho thy di nh hng ca phc GMoN lm tng cng b my quang hp, cng quang hp cng nh cng h hp to nng lng cho cc hot ng ca cy so vi i chng. 3.2.4. nh hng ca phc GMoN n nng sut ca cy u tng Nng sut thu hoch ca cy u tng di nh hng phc GMoN c trnh by bng 4. Kt qu cho thy s lng qu/cy, s lng ht/cy, trng lng ht/cy l th nghim c x l phc GMoN u cao hn i chng. iu ny cho thy hot tnh sinh hc ca phc GMoN c hiu qu i vi i sng cy trng.
Bng 4. nh hng ca phc GMoN n nng sut ca cy u tng

Ch tiu theo di S qu/cy S ht/cy Trng lng ht/cy (g)

i chng x m 44,0 3,2 166,8 8,7 33,4 1,8 CV% 4,91 3,57 6,13 x m 57,3 4,5 211,2 7,4 40,2 2,1

Phc GMoN CV% 3,65 4,27 7,04 % so vi C 130,23 125,12 120,36

3.2.5. nh hng ca phc GMoN n phm cht ht u tng i vi cy u tng, hm lng protit v lipit trong ht l cc ch tiu v cng quan trng khi nh gi cht lng ht thu hoch c. Phn tch cc ch tiu ny,
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TP CH KHOA HC V CNG NGH, I HC NNG - S 5(40).2010

chng ti thu c s liu trnh by bng 5. Kt qu cho thy cht lng ht u tng c ci thin khi x l vi phc GMoN.
Bng 5. nh hng ca phc GMoN n cht lng ht u tng

i chng Ch tiu theo di x m CV% x m

Phc GMoN CV% % so vi C 112,28 115,32

Hm lng protein (%) Hm lng lipit (%) 4. Kt lun

41,62 0,92 18,76 0,19

3,21 5,38

46,73 0,87 21,53 0,13

4,15 6,13

1. nghin cu s to phc a phi t gia ion t him Nd3+ vi axit Lglutamic v natri molypdat. kho st cc yu t nh hng v tm c cc iu kin ti u v nhit , thi gian, pH v t l cc cht tham gia phn ng tng hp phc rn a phi t glutamat molypdat neodim. 2. Bng cc phng php phn tch nhit vi sai, quang ph hng ngoi xc nh c thnh phn ca phc v cng thc phn t ca phc rn l Nd(HGlu)(MoO4).2H2O. 3. Vic to phc gia ion t him neodim v nguyn t vi lng Mo c tc dng tt n i sng cy u tng: lm tng cc ch tiu sinh trng pht trin, tng cng cc qu trnh sinh l theo hng thun li; tng nng sut v cht lng ht. TI LIU THAM KHO [1] Ng Th Dn, Trn nh Long, Trn Vn Li, Th Dung, Phm Th o, Cy u tng, NXB Nng nghip, H Ni, 1994. [2] Phm Vn Hai. Nguyn Tn L, Tng hp phc cht glutamat borat neodim v th nghim lm phn bn vi lng cho cy vng, Tp ch Khoa hc v Cng ngh i hc Nng, s 2 (31), tr. 66-73, 2009. [3] Nguyn Xun Trng, Phn bn vi lng v siu vi lng, NXB Nng nghip, Thnh ph H Ch Minh, 2005. [4] Nguyn Trng Uyn, Nguyn nh Bng, Nghin cu hot tnh sinh hc ca to phc trong nng nghip, Tp ch Khoa hc trng i hc KHTN-HQG H Ni, s 4, tr. 19-23, 1995 [5] Yang Li., Journal of baoji college of Arts and Sciences, Vol. 18, No. 1, 1998 [6] Yang Zupei, Zhang Banglao, Yu Yueping, Zhang Hongyu. Journal of Shaanxi Normal University, Vol. 26, No. 1, 1998 .
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