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T A P CHI H O A HOC 7 . 5 1 ( 6 ) 7 4 0 - 7 4 3 T H A N G 12 N A M 2013

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CHE TAO VANG NANO VA D\tU CHJNH TANG KJCH THUdC SU" DUNG HAT MAM BANG PHUONG PHAP CHIEU XA GAMMA Co-60

N g u y i n Q u o c H i e n ' , D a n g V a n Phii', B u i D u y Du^*

' Trung tdm Nghien ciiu vd Triin khai Cdng nghe Birc xg. Viin Ndng lugng nguyen lir Viet Nam ' Viin Khoa hoc Vdt lieu img dung, Vien Hdn lain Khoa hgc vd Cdng nghi Viet Nam

Den Tda soan 3-7-2013

Abstract

Gold nanoparticles with the size in the range 8-20 nm were synthesized by '/-irradiation of Au^' solution contaimng polyvinyl pyrrolidone as stabilizer. The size of gold nanoparticles was increasingly further regulated from 20 up to about 60 nm using seed enlargment method. The gold nanoparticles were characterized by UV-vis spectroscopy and transmission electron microscopy (TEM). The colloidal gold nanoparticles with the size from 8 to 60 nm have a plasmon absorption band with maximum wavelength in the range 517.5-543.0 nm. The colloidal gold nanoparticles soluUons storaged at room temperature were stable for months

Keywords: Gold nanoparticles, irradiation.

1. M O DAU 2. T H U C N G H I E M

T r o n g cac cdng trinh t r u d c day chimg tdi da nghien ciru che tao v a n g n a n o b a n g p h u o n g phap chieu xa su dung chitosan, alginat lam chat dn dinh va khao sat imh h u d n g ciia n d n g dp Au^' den kich thudc ciia hat vang nano [ 1 , 2 ] . Nhieu p h u o n g phap khac nhau d u g c nghien ciru de che tao vang n a n o , trong dd p h u a n g p h a p chieu xa cd mdt sd uu diem nhat dinh so vdi p h u a n g phap hda hgc truyen t h d n g va cac p h u a n g phap khac [1-3], Hon nii'a, chieu xa g a m m a d u g c xem la mot phirong phap xanh (green route) de che tao hat nano kim loai [4]. V a n g nano cd kich thudc trung binh nhd hon 5 nm d u a c diing dc che tao vat lieu xiic tac hieu n a n g cao [5, 6]. T u y nhien, kich t h u d c hat vang n a n o nhieu khi yeu cau ldn hon de iing d u n g trong ITnh vuc sinh y hpc va cac ITnh vuc khac. N g h i e n cii'u ciia Chilhrani et al cho thay kich thudc tdi uu d e hat vang n a n o hap thu vao tc bao la 50 nm [7]. B h u m k a r et al. da su d u n g hat vang nano vdi kich t h u d c 10-50 nm d e van chuyen insulin [8], El-Sayed et al sir d u n g hat v a n g nano kich thudc 30-40 nm de chan doan va dieu tri ung thu [9].

T r o n g bai bao nay chiing tdi trinh b a y ket q u a nghien cuu che tao vang n a n o vdi chat dn dinh la PVP va dieu chinh gia tang kich thirdc sir d u n g hat mam bang p h u o n g phap chieu xa 7C0-6O.

2 . 1 . N g u y e n lieu, hda chat

H A u C U , polyvinyl p y r r o l i d o n ( P V P K90) va n u d c la san p h a m tinh khiet cua Merck, Diic.

Isopropanol loai tinh khiet ciia T r u n g Q u d c . 2.2. P h u o n g p h a p

2.2.1. Chudn bi mau vd chieu xg

H d a tan P V P vao n u d c t a o d u n g djch PVP 2% (2 g/IOO ml). H d a tan H A u C U vao n u d c tao dung djch A u ' " 10 m M . Tir d u n g djch P V P 2 % , Au^^ 10 mM va isopropanol tao c a c d u n g djch vdi ham luong P V P la 1%, isopropanol 5 % (v/v) va n d n g do Au^* ta 0,25; 0,5 va 1 m M . D u a d u n g djch Au^"^ vao lg thuy tinh cd nut van kin va sue khi n i t o khoang 10 phut.

Chieu xa d u g c tien h a n h tren ngudn gamma S y S T / C o - 6 0 / B tai T r u n g t a m V I N A G A M M A vdi lieu xa 4 kGy ddi v d i m a u Au^*^ 0,25; 0,5 mM va 8 k G y ddi vdi m a u Au^* 1 m M .

D u n g djch v a n g n a n o tir m a u Au^^ 1 mM du(:rc su d u n g lam hat m a m d e dieu chinh tang kich thucrc hat. T h a n h p h a n d u n g dich d u g c chuan bi nhu sau:

lay mdt phan the tich d u n g dich v a n g n a n o (Au**) 1 m M p h a trdn vdi 4, 8, 12, 16 va 2 0 p h i n t h i tich d u n g djch A u ' * 1 m M . T o n g n o n g dg vang

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TCHH.T. 51(6).2013

([Au'']+[Au'*]) trong dung djch la 1 mM va ti le nong do iAu'*]/[Au'*] la 4; 8; 12; 16 va 20.

2.2 2. Do phd UV-vis

Mau sau khi chiiu xa de dn dinh qua dem. Pha loang dung djch keo vang nano bang nudc den ndng dp 0,1 mM. Do phd UV-vis fren may UV-2401PC, Shimadzu, Nhat ban, diing cuvet thach anh 1cm.

Theo ddi dp dn dinh (phd UV-vis) cua dung dich keo vang nano theo thdi gian luu giir tai nhiet do phdng

2 2.3. Chup dnh TEM

Anh TEM cac mau vang nano dugc thuc hien tren may JEM 1010, JEOL, Nhat Ban. Kicli thudc hat trung binh va phan bd kich thudc hat dugc xac dinh tir anh TEM (~ 200 hat/mau) vdi su hd trg ciia phan mem photoshop CS2, Version 9.0 va thuat loan xu ly thong ke.

Bdi Duy Du vd cdng su 3. KET QUA VA THAO LUAN

3.1. Anh hudng cua ndng do Au'* den kich thudc hat vang nano

Phd UV-vis cua dung djch vang nano che tao tir cac miu vdi ndng do Au''"' la 0,25; 0,5 va 1 mM dugc trinh bay tren hinh 1. Ket qua cho thay birdc sdng hap thu cue dai (Xn^O cua dung djch vang nano 0,25; 0,5 va 1 mM tuong irng la 517,5; 523,5 va 529,5 nm. Anh TEM va do phan bd kich thudc hat ciia mau vang nano tren hinh 2 cho thay kich thudc hat trung binh (d, nm) tang theo ndng do Au^" (bang 1). Ket qua nhan dugc kha phu hgp vdi ket qua trong cdng trinh trudc day cua chiing tdi ve che tao vang nano sii dung alginat lam chat dn dinh [2]. Nghien Cliu cua Li et al ve che tao vang nano bang chieu xa gamma Co-60 su dung PVP lam chat dn dinh va ndng do Au'"' tir 0,2 den 2 mM cung cho thay kich thudc hat vang nano tang theo ndng dd cua Au'*

[10],

Bdng 1: Dac trung ciia keo vang nano theo ndng do Au'""/PVP 1%

Au^*, mM 0,25

0,5 1,0

^ x , nm 517,5 523,5 529,5

OD 0,59 0,46 0,40

d, nm 8,7±0.3 13,7±0,7 20,5±2,1

Hinh 1: Phd UV-vis ciia vang nano/PVP 1% vdi ndng do Au"; (a) 0,25 mM; (b) 0,5 mM va (c) 1 mM 3.2. Dicu chinh tang kich thudc hat vang nano

hing phuxmg phap phat trien hat mam H?t vang nano tir miu Au'* 1 mM/PVP 1% vdi kich thudc trung binh 20,5 nm dugc sir dung lam hat

mam de dieu chinh tang kich thudc hat. Trong phuang phap nay, cac hat mam ddng vai Ird la tam phat trien kich thudc hat va kich thudc se tang dan do su khii cac ion Au" hap phy Ien be mat hat mam (cluster). Khi ti I? [Au'']/[Au"] tang lir 4 dkn 20 lin

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TCHH T 51(6), 2013 Che tgo vang nano va dieu chinh...

thi X,„. ciia vang nano djch chuyjn vi phia c6 birdc cua hat vang nano tang tir 20,5 nm (hat mam) den song lon hon. cii thj ia tit 529,5 nm (hat mam) din 61,4 nm([Au'"l/[Au°l = 16, ! „ . . = 543 nm).

546 nm ([Au'']/[Au°] = 20) va Mch thuoc trung binh

• ' •

a n jii_

26 30.14 38 42

Hinh 2: Anh TEM vii phan bd kich thudc hat vang nano/PVP \% Iheo ndng dp Au'' 0, 25 mM (A. a): 0,5 mM (B, b) va 1 mM (C, c)

S 12 16 [Au^-]/[ALi']

Hinh 3: Tuong quan giira ^,a\ va kich thudc hat d ciia vang nano theo ti te [Au'"*"]/[Au'']

Kich thudc trung binh ciia hat vang nano che tao vang nano thu dugc tuong ddi phii hgp vdi ket qui dugc d6i vdi mau [Au'^]/[Au*'] = 8 va [Au"]/[Au°] = tinh bing cdng thirc: dhai= d^^m (1+ [Au'*]/[Au'^)' 16 tuong ung la 46,8 nm va 61,4 nm. Kich thudc hat la 42,6 va 52,7 nm [11]. Kit qua vk gia tang klcb

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TCHH, T. 51(6), 2013

thudc hat cd phan khac so vdl ket qua trudc day ciia chiing tdi ve che tao vang nano bang birc xa sir dung alginate lam chit dn dinh [2]. Chimg tdi cung ap dgng phuang phap phat trien mam de gia tang kich thudc hat, tuy nhien kich thudc hat vang nano chi tang tir 20 nm (hat mam) den 40 nm ddi vdi [Au'']/[Au''] = 6 va khi [Au'1/[Au''] = 8 thi kich thudc hat khdng tiep tuc tang Ien ma cdn xuat hien them nhii'ng hat mdi vdi dudng kinh nhd hon 10 nm.

Nguyen nhan cd the la chat dn dinh khac nhau anh hudng den qua trinh gia tang kich thudc hat bang phuang phap phat trien hat mam. Henglein et al, cung da nghien ciiu sir dung phuang phap phal trien hat mam de gia tang kich thudc hat vang nano su dung citrat lam chat on dinh va gia tang kich thudc hat theo kieu bac gap ddi tir 15 den 30 nm rdi dimg hat 30 nm lam hat mam de gia tang Ien 60 nm, tiep luc dimg hat 60 nm lam hat mam gia tang Ien 120 nm [12]. Nhu vay, cd the lua chpn kfch thudc hat vang nano ban dau trong khoang 8 den 60 nm de gia tang kich thudc gap ddi vdi do phan bo kich thudc dong deu han.

Mat do quang ciia dung dich vang nano hau nhu khdng ddi trong 6 thang luu giir tai nhiet dp phdng, chirng to vang nano che tao dugc cd do on dinh tdt.

4. KET LUAN

Da nghien ciru che tao vang nano bang phuong phap chieu xa gamma Co-60 su dung PVP lam chat dn dinh. Kich thudc hat vang nano nhan dugc trong khoang 8-20 nm va dieu chinh gia tang tir 20 nm (hat mim) d6n 60 nm. Dung dich vang nano/PVP che tao dugc cd dg dn dinh tdt.

TAI LIEU THAM KHAO

1 Nguyen QuSc Hi^n va cs. Che tao vdng nano bdng

Bui Duy Du vd rdng su phuang phdp chieu xa. Tap chi Hoa hoc, 47 1 "-;-179 (2009)

2. N. T. Anh, D. V Phu, N N. Duy, B. D. Du, \ Q, Hien. Synthesis of alginate stabilized gold nanoparticles by y-irradialion with controllable size using different Au * concenti-a-tion and seed parti- cles enlargement, Rad. Phys Chem., 79. 405-408 (2010).

3. S A. Dong, S. P Zhou. Mater. Sci, Eng B, 140, 153 -159(2007).

4 M. Chandra, P. K Das. Green routes to noble metal nanoparticle synthesis. Inter J Green Nanotech Phys C h e m , l , 10-25(2009)

5. A.K. Sinhaa, S. Seelana, S. Tsubotaa, M. Harutab.

Calalysis by gold nanoparticles. epoxidation of propene. Top. Catal, 29, 95-102 (2004).

6 M B . Cortie, E. van der Lingen. Catalytic gold nano- particles. Mater. Fomm, 26, 1-14 (2002).

7. A. D. Chilhrani, A. A. Ghazani, W. C, W. Chan.

Determining the size and shape dependence of gold nanoparticle uptake into mammalian cells, Nano Letters, 6, 662-668 (2006).

8. D. R. Bhumkar, H. M Joshi, M SasUy, V B Pokharkar Chitosan reduced gold nanoparticles as novel carriers for transmucosai deliveiy of insulin, Pharma, Res,, 24, 1415-1426 (2007).

9. L H El-Sayed, X Huang, M A El-Sayed Selective laser photo-thermal therapy of epithelial carcinoma using anti-EGFR antibody conjugated gold nanoparticles. Cancer Letters, 239, 129-135 (2006).

10. T. Li, H. G. Park, S. H. Choi y-lrradialion-mduced preparalion of Ag and Au nanoparliclei and their characterizations. Mater Chem. Phys,, 105, 325-330 (2007).

1 i G. Schmid. Large clusters and coiloids-metals in the embiyonic state, Chem Rev , 92, 1709-1727 (1992) 12 A. Henglein. D, Meisel. Radioiytic control of the size

of colloidal gold nanoparticles, Langmuir, 14, 7392- 7396(1998).

Lien he: Biii D u y Du

Vien Khoa hgc Vat lieu U'ng dung, Vien Han lam Khoa hgc va Cdng nghe Vi^t Nam S6 1 Mac DTnh Chi, quan 1, Thanh phd Ho Chi Minh Email: [email protected]; dien thoai: 0976743030.

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