TAP CHI HOA HOC T. 50(4) 461-465 THANG 8 NAM 2012
CHI^U XA VAl COTTON TRONG DUNG DICH AgNOj D^ CH^ TAO VAl KHANG K H U A N
Truwng Thi H^nh", D§ng Van Phii, Nguyen Thj Thu, Nguyen Quoc Hien Trung tdm Nghiin ciru vd Triin khai Cdng ngh^ Buc xg, VAEC
Den Tdasogn 3-4-2012
Silver nanoparticles (AgNPs) with diameter about 8 nm were immobilized on the surface of cotton fabrics by y-irradiation of fabrics in the AgN03 chitosan solution. Effect of absorbed dose on immobilization of the AgNPs on fabrics was investigated. The optimal dose was selected to be 13,8 kGy at concentration of AgNOj was 1.5 mM in 1%
chitosan solution. The maximal content of AgNPs on fabrics was of 1696 mg/kg. The presence of AgNPs on fabrics was confirmed from scanning electron microscopy (SEM) images and X ray diffraction (XRD) patterns. The antibacterial activity of coHon-AgNPs fabrics after washings against S. aureus and E. coli was found to be 99.99%. In addition, the AgNPs fabrics were innoxious to the skin (k=0) after I, 5, 10, 20, 30 and 40 washings by skin-imtation testing to animal (rabbit).
Keywords: Silver nanoparticles, coRon fabrics, chitosan, antibacterial, y-irradiation.
1. MO DAU
Che tao vd nghien cdu cdc dac trung ciia keo bac nano da dugc chu y bdi nhieu nhd khoa hgc trong nhiing thgp ky qua bdi chirc nang ndi bat va nhirng ling dyng hiru hieu cua vat lieu nay. Ciing nhu cdc kim logi nano khdc, bgc nano cd the che tgo bang nhieu phucfng phdp nhu khu hda hgc, quang hda, dien hda, biirc xa nhiet vi sdng.... Tuy nhien, sir dyng hire xg gamma hay EB de che tao kim logi nano dugc ddnh gid la phuang phdp mdi vd than thien mdi trudng, ddng thdi sdn pham cd dp tinh khiet cao va kich thudc hgt dn djnh [I, 2]. Cho den nay, nhieu sdn pham thiet yeu trong cugc sdng sinh boat hang ngay chira bac nano da vd dang dugc thuang mgi hda. Hai mang nghien ciru dugc quan tam nhieu nhdt dd Id vat lieu gan bgc nano cho muc dich sat khudn va cho dich vu y te. Ngdy nay, khi nhu cau chdm sdc sue khde ngdy cdng tang thi cac logi vdi sgi khdng th6 thieu vang tinh nang khdng khuan. Khd nang khdng khudn ciia cac logi vdi sgi gan bac nano da dugc minh chung bdi mgt sd tac gid.
Hieu ling khdng khudn doi vdi 5*. aureus va E. coli Id 99,90% khi vai dugc gdn bac nano kich thudc ~3 nm.
Logi vai nay cung khong gay dgc tinh cho da khi thir nghiem tren viing da trdy sudt cua thd [3]. Dgc tinh khdng khudn ciia vdi sgi gan bgc nano cung dugc chiing td bdi Dubas khi cd djnh bgc nano- poIy(methacrylic acid) len sgi nilon va cotton, hieu lye diet khudn S. aureus ddn 80% [4]. Thir nghipm
ldm sdng ddi vdi bpnh nhdn bj bpnh eczema da giam rd ret sau hai tuan mac vdi gan bgc nano [5]. Su luu giii bac nano tren vdi dS duy tri kha ndng khdng khudn Id vdn d^ cdn dugc q_uan tdm. Trong cdng trinh ndy, vdi vdi cotton gan bac nano (cotton- AgNPs) bang each chieu xg ddng thdi vdi va dung dich AgNOa, hdm lugng bgc nano tren vdi van dn dinh qua 40 Ian gigt. Nhd vay, hogt tinh khdng khudn vdn dgt -99,99% cho hai chiing S. aureus va E. coli sau 40 ldn gigt.
2. THI/C NGHIEM
2.1. Che tao vai cotton-AgNPs bang each chieu xa ddng thM vai trong dung dich AgNOa Khodng 60 g vdi cotton trdng (120 g/m^) dugc gigt, roi chieu xg cimg 500 ml dung djch AgNOs ndng dp 1,5 mM trong chat dn dinh chitosan 1%, trong khodng lieu xa tir 5-20 kGy. Tilp theo, vdi chilu xa dugc sdy khd tai 70'*C trong 15 phut. Sau dd, mlu dugc gigt va say khd de xdc dinh ham lugng bac nano cdn lai tren vai qua cac ldn gigt.
Hdm iugng bgc nano tren vai dugc xac djnh bang phd phat xg nguyen tiJr cam irng plasma (inductively couple plasma atomic emission spectroscope ICP-AES), model Optima 5300 DV (Perkin Elmer) sau 1, 5, 10, 20, 30 va 40 Idn giat
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2.2. Dac trung ciia vai colion-AgNPs
Sy cd mgt ciia bgc nano tren sgi dugc xac nhgn bdi dnh chyp SEM (Scanning Electron Microscopy), model JSM-6480LV, vdi the gia toe 10 kV vd dg phong dgi 5.500 lan. Phd nliicu \g tia X ciia nhitng mau vai gdn bgc nano dugc do tren IliicI bj nhicu xg Shimadzu 5A, vdi nguon \g CUKQ (35 kV and 25 mA), toe dg quet 0.57phut tir 5-70° (20). Kich thudc hgt cho tinh the hinh cau dugc tinh iheo cdng thirc Debye-Scherrer:
D = 0,94Wpcose (1)
Trong dd, D kich thudc trung binh hgt tinh the bgc nano. X = 0,15406 nm budc sdng ciia biic xg CuKu, p Id dp rgng ban eye dgi ciia vgch nhieu xg trung tdm, 0 la gdc Bragg [6].
2.3. Hoat tinh khdng khuan \ a thir nghipm kich irng da ciia vai cotlon-AgNPs
Hogt tinh khdng khudn ciia \ai gdn bgc nano qua 1, 5, 10, 20. 30 va 40 ldn gi^t dugc thir nghipm vdi hai chiing vi sinh Staphylococcus aureus vd Escherichia coli. Qui trinh thir nghipm theo Tieu chuan Dugc dien Viet Nam III [7]. Mau vdi khoang Ig dugc xir ly vdi 10 ml djch khuan, ndng dp ~10 tl bao/mt, trong klioang 30 phiit. Xac djnh khd nang sdng ciia vi sinh bang each dem sd khuan Igc tren dia.
Hieu irng khdng khuan dugc tinh:
Tnrcmg Thi Hanh vd cgng st^r AgNOs, electron hydrat hda (e'aq) va goc hydro H*
dugc phdt sinh tir sy xg ly nude dd khir ion Ag* tren be m$t sgi tgo nguyen tii Ag. Nhiing nhdm 'OH co the phdn img vdi nhOng phan tii chitosan logi trir hydro vd tgo goc chitosan. Nhitng goc ndy cung tham gia phdn irng khir Ag* tgo Ag . Cdc nguyfin tiJr bgc tren be mjt sgi tilp tyc phdn irng vdi nhiing ion Ag' trong dung djch tgo cdc "cyin" (cluster) nguydn tir Ag tren be m^l sgi. Cdc phdn irng dugc de nghj nlursau:
Ag' + e„q - Ag" (3) Ag' + H* — Ag" + H* (4) tClIiiO^N],, (Chitosan) + 'OH - •
[C6H||04N]„.,[C6H|oO,.N]* + H2O (5) Ag • + C6HM04N]„.,[C6H,o04Nr -»
Ag''+ [CflHn04N]n.i[C6H904N] + H* (6) nAg"-* Ag2 -* ... Ag„ (7) I .icu hap thy ddng vai trd quan trgng cho sy tgo vd phdt trien hgt keo bgc nano bdi phugng phap chieu xg. C) lieu thap hat nano chua dugc hinh thanh, tuy nhien neu lieu xg qud cao s€ tgo kich thudc qua Idn hodc kit liia [9], Trong hinh I hdm lugng bgc nano tren vdi khdng bien ddi nhieu trong khoang lieu 4-10 kGy nhung tdng d nhiing lieu xg cao hon.
Lugng bgc nano cd djnh tren vai da dgt gid trj eye dgt tgi 1696 mg/kg, khi chieu xg vai ddng thdi voi dung djch AgN03l,5 mM, tgi lieu xg 13,8 kGy. Day Id lieu xa tdi uu dugc Iga chpn cho hp phan irng nay.
IO0x(No-N,)/No (2)
Trong dd: No, N, Id sd khuan lac trong dia ddi chiirng va dTa cd mau thi nghiem.
Thii dgc tinh tren da theo hdm Iugng bgc nano dugc kiem djnh tgi Trung tam kiem nghipm thudc theo tieu chudn is6-10993-l0: 2002 [8]. Thi nghipm tien hanh d nhipt dp phdng 25±3'^C, dg am tuong ddi 30-70%, dnh sdng ddm bdo 12 gid tdi, 12 gid sang hang ngdy. Sir dyng thd trudng thdnh, khde mgnh, can ngng tren 2 kg, nhdt rieng va nudi dudng trong dieu kipn thi nghipm 5 ngdy trudc khi thir. Ldm sgch ldng thd d viing lung, hai ben cpt sdng, mgt khoang 10x15 cm, mdi mau dugc thii vdi 3 thd. Dgt mdu vai da gan bac nano len da. Quan sat vd ghi diem phdn irng tren chd da dgt chdt thu d cdc thdi diem 12, 24, 48 va 72 gid.
3. KET QUA VA THAO LUAN 3.1. Chetaovai cotton-AgNPs
Lieu x((kG)|
Hinh I • Anh hudng ciia lieu xg den ham lugng bgc nano gan len vai 3.2. Dac trirng ciia vai cotton-AgNPs
Sy hipn dipn cua bac nano tren vdi dugc xac nhgn qua dnh chyp SEM. Trong hinh 2a, be mat vai tran, phang, sau khi gdn bgc nano nhirng hgt nho h ti phdn bo kha deu tren be mat vdi chOrng td rdng da co sy gdn ket dong bg cCia nhiing hgt bac nano d do.
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hipn phdn ung la thich hgp. Gian do tia X cCia mdu vdi gdn bgc nano so vdi mdu vdi trdng bieu thj trong hinh 3. Cdc dinh tai cdc vi tri 2 theta 14° vd 22° ddc tnmg cho cau true ciia polysacharit nhu xenlulo, chitosan [10]. Sau khi gdn bgc nano mlu vdi cd thSm cdc dinh mdi tgi cdc vj tri 2 theta 38,63°, 43,28°, 62,46° va 76,32°tuang ijmg vdi cdc m§t phdng (111), (200), (220) vd (311) ciia cku triic l§p phuang tam mat ciia tinh thi bgc (hinh 3b). Ket qua ndy phii hgp vdi kit qud ciia mpt so tac gid khdc khi khdo sdt nhieu xg tia X cua bgc nano [11, 12]. Trong nghien cijru nay, kich thudc hgt bgc nano ~ 8 nm dugc xdc djnh theo cdng thiic Debye - Scherrer (1).
Chieu xg vdi cotton trong dung dich ...
trong polyvinylpirrolidone phdn tan tren bl mgt vdi bdng cdch ep vdt, roi ldm khd d nhipt dg 90-I00°C trong 3-4 phiit, sau dd xijr ly d nhipt dg 130°C. Sau 5 lan gigt, chi so ben gidt dugc xdc djnh theo ti so giira hdm lugng chkt khdng khuan trudc vd sau khi gigt trenvdila52%[13].
20, dp
S ^ ^ W N W V ^ . A * ^ ' ^
(VF*^'J
Hinh 2: (a) Anh SEM cua vdi cotton, (b) ciia vai cotton-AgNPs
3.3. Hoat tinh khang khu4n va thir nghipm kich iimgda
Trong qua trinh xir ly vdi khdng khudn ngoai myc tieu gan chdt khang khudn len vai thi dg ben khang khudn ciia vdi trong aua trinh sir dyng ciing la mpt myc tieu quan trgng can phdi dgt dugc. Trong che tgo vdi gdn bac nano can cai tien cac dieu kipn phan ling dl lien ket giGa bgc nano va phan tu xenlulo vdn ben qua nhieu \kn gigt. Phuang phdp dugc sir dgng phd biln hi$n nay la co djnh bgc nano da ben-hda polyme ISn vai d nhipt dg cao (70-120°C) [3]. Bgc nano vdi n6ng dg l-5g/dm^ dugc ben hda
20, dg
Hinh 3 • Gidn dd nhilu xg tia X ciia (a) vai cotton, (b) vdi cotton-AgNPs
Cd djnh bgc nano bdng phuang chilu xg ddng thdi vdi trong dung djch AgNOj la mgt phuang phap mdi vd rat tien Igi, khi qua trinh khu vd ben hda hgt bgc nano tren vai xdy ra ddng thdi. Neu sir dyng chat ben hoa chitosan, tren vdi AgNPs khdng chi cd cdc lien kit Ag-0, md cdn cd lien kit hydro giira nhirng nhdm -OH va cac nhdm amit -NH-CO- hogc amin - NH2 cua xenlulo va chitosan. Nhd do, khd ndng gdn ket bgc nano len vdi dugc tang cudng. Ket qud trong bdng 1 da cho thiy lugng bac nano tr6n vai da thay doi qua lan gidt ddu tien, nhung da dn djnh cho nhiing ldn gigt tilp theo. Cac ky hipu Co-Ago, Co- Agi, Co-Ags, Co-Agio,_ Co-Ag2o, Co-Agso vd Co- Ag4obilu thj cho cac mdu vdi gdn bgc nano ban ddu vd da gigt 1, 5, 10, 20, 30 va 40 ldn. Sau 40 Ian gigt, lugng bgc nano vdn luu gi& 858 mg/kg ddng thdi cd
TCHH, T. 50(4), 2012
hi^u irng khdng khukn din 99,95 vd 99,98 %, tuang img cho hai chiing S. aureus vd E. coli. Gupta P. vd cgng sy dd xdc nh§n lugng AgNPs nhu Id chia khda dilu chinh hogt tinh khdng khu^n 114]. COng th6m, dudng kfnh bgc nano ciing Id ylu to quan trgng, Lee cung da chdng minh hi$u i>ng khdng khu4n cOa bgc nano dudng kInh 2-3 nm t6t ban bgc nano dudng kinh 30 nm [3]. Qua kit qud trong bdng 1 chumg td bgc nano dudng kInh - 8 nm dfi chi tgo Id thIch hgp cho myc dich khdng khu^n.
Truong Thf Hgnh vd cgng sir Thii nghi$m d^c tinh trSn da thd do Vi§n kiem nghi§m thu6c Thdnh ph6 Hb Chf Minh tiin hdnh theo tidu c h u k ISO-10993-10: 2002 [8]. Ket qud cho thky rflng, vdi cdc thd dugc thi nghl$m d viing da dugc ddp vdi gdn bgc nano dd khdng cd sg tgo vdy vd ban dd, cQng khdng gdy phii nl so vdi vCing da kl bSn khdng ddp chSt thi>. Cdn cii- vdo bdng dilm phdn img vd qud trinh theo dOi tinh trgng da, phdng dugc t:^ cda Vi$n kilm nghiem thudc dd kit lu|n m3u vdi thir nghiem dd khdng gdy kich irng da vdi k=0.
Mau
Co-Ago Co-Agi Co-Ags Co-Agio Co-Ag2o Co-Ag3o Co-Agio
Table 1:
S6l4n gijt
0 1 5 10 20 30 40
hli^u img khing khuSn cua vAi cotton-AgNPs v& di^m thir kfch img da Lu(?ng
AgNPs trgn v4i, mg/kg
1696 1034 1024 910 880 860 858
Hilu img khdng khudn, % S. aureus
100 99,94 99,99 99,94 99,99 99,99 99,95
E. coli 100 100 100 100 100 100 99,98
Dilm phdn img G9y ban d6
0 0 0 0 0 0 0
PhiinJ 0 0 0 0 0 0 0
Kit 1u$n Khdng kich (hig da
(k=0) Khdng kfch iing da
(k=0) Khdng kfch img da
(k=0) Khdng kfch img da
(k=0) Khong kfch img da
(k=0) Khdng kfch img da
(k=0) Khdng kfch img da
(k=0) Khdng kfch img da
(k=0) 4. KET LUAN
B^ chi tao dugc vdi cotton-AgNPs vdi kfch thudc hgt ~ 8 nm bdng cdch chilu xg vdi cotton trong dung djch AgNOj 1,5 mM, tgi 13,8 kGy trSn ngudn gamma Co-60.
Nhiing djc tnmg ciia bgc nano tr6n be m^t sgi dugc xdc nhan qua anh chyp SEM vd phd nhiSu xg tiaX.
Vdi hdm lugng AgNPs tren vdi ban d4u Id 1696 mg/kg, sau 40 Idn gigt lugng AgNPs luu giti dugc Id 858 mg/kg. Vdi lugng nay hogt tfnh khdng khu4n vdn dgt 99,95 vd 99,99% cho hai chung S. aureus vd E. coli. Ket qud thii kich img da tr6n dgng vdt (thd), cho cac mdu vdi gdn bgc nano sau 1, 5, 10, 20, 30, 40 ldn gigt cd hp sd k = 0. Cdc miu vdi cotton- AgNPs da khong gay kich iing da. Nhu vgy, vdi dd che tao cd the sii dyng dl may Vhk\i trang khdng
khuan, ho$c may trang phyc cho nhan vien lam vi&
trong mdi trudng dl bj vi khudn thdm nhgp.
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Lien he: Trinmg Thi H^nh
Trung tdm Nghien ciru vd Triln khai Cdng nghp Biirc xg, VAEC 202A, dudng 11, phuong Linh Xuan, Thii Diic, Thanh pho Ho Chi Minh Email: [email protected]
Dien thogi: 0906628311
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