Professional Documents
Culture Documents
M u
Vt liu nano ang i su vo i sng hin i v ang dn dn chim mt ngha rt ln i vi i sng ca con ngi nh vo cc tnh cht rt c bit ca chng m cc vt liu truyn thng trc khng c c. Tnh c bit ca vt liu nano c c l nh kch thc nh b ca chng. Bt c vt liu no u c s hng ng vi t trng ngoi (H), th hin bng t ha (t - M). T s c = M/H c gi l cm t. Ty thuc vo gi tr, cm t c th phn ra lm cc loi vt liu t khc nhau. Vt liu c c < 0 (~ -10-6) c gi l vt liu nghch t. Vt liu c c > 0 (~10-6) c gi l vt liu thun t. Vt liu c c > 0 vi gi tr rt ln c th l vt liu st t, ferri t. y, vt liu t tnh ng l vt liu st t, ferri t hoc siu thun t. Ngoi cm t, mt s thng s khc cng rt quan trng trong vic xc nh tnh cht ca vt liu, v d nh: t bo ha Ms (t t cc i ti t trng ln), t d Mr (t cn d sau khi ngng tc ng ca t trng ngoi), lc khng t Hc (t trng ngoi cn thit mt h, sau khi t trng thi bo ha t, b kh t). Nu kch thc ca ht gim n mt gi tr no , ph thuc vo tng vt liu c th, tnh st t v ferri t bin mt, chuyn ng nhit s thng th v lm cho vt liu tr thnh vt liu siu thun t. i vi vt liu siu thun t, t d v lc khng t bng khng. iu c ngha l, khi ngng tc ng ca t trng ngoi, vt liu s khng cn t tnh na, y l mt c im rt quan trng khi dng vt liu ny cho cc ng dng y sinh hc. Trong t nhin, st (Fe) l vt liu c t bo ha ln nht ti nhit phng, st khng c i vi c th ngi v tnh n nh khi lm vic trong mi trng khng kh nn cc vt liu nh -xt st Fe3O4 c nghin cu rt nhiu lm ht nan t tnh.
2. Ch to ht nan t tnh n l
2.1. Phng php nghin
Phng php nghin c pht trin t rt sm ch to ht nan t tnh dng cho cc ng dng vt l nh truyn ng t mi trng khng kh vo bung chn khng, lm cht dn nhit trong cc loa cng sut cao,... Trong nhng nghin cu u tin v CLT, vt liu t tnh -xt st Fe3O4, c nghin cng vi CHHBM (a-xt Oleic) v dung mi (du, hexane). CHHBM gip cho qu trnh nghin c d dng v ng thi trnh cc ht kt t vi nhau. Sau khi nghin, sn phm phi tri qua mt qu trnh phn tch ht rt phc tp c c cc ht tng i ng nht. Phng php nghin c u im l n gin v ch to c vt liu vi khi lng ln. Vic thay i CHHBM v dung mi khng nh hng nhiu n qu trnh ch to. Nhc im ca phng php ny l tnh ng nht ca cc ht nan khng cao v kh c th khng ch qu trnh hnh thnh ht nan. Ht nan t tnh ch to bng phng php ny thng c dng cho cc ng dng vt l.
Hnh 2: C ch hnh thnh v pht trin ht nan trong dung dch C ch tng hp ht nan Fe3O4 nh sau: vi t phn mol hp l Fe3+/Fe2+ = 2 trong mi trng kim c pH = 9 14 v trong iu kin thiu xy. Fe3+ + H2O Fe(OH)x3-x (thng qua qu trnh mt proton) Fe2+ + H2O Fe(OH)y2-y (thng qua qu trnh mt proton) Fe(OH)x3-x + Fe(OH)y2-y Fe3O4 (thng qua qu trnh xi ha v dehydride ha, pH > 9, nhit 60). Tng hp cc phn ng trn chng ta c phng trnh sau: Fe2+ + 2Fe3+ + 8OH- Fe3O4 + 4H2O Nu c oxi th magnetite b oxi ha thnh hydroxide theo phn ng: Fe3O4 + 0,25 O2 + 4,5 H2O 3Fe(OH)3
2.3. Vi nh tng
Vi nh tng (microemulsion) cng l mt phng php c dng kh ph bin to ht nan. Vi nh tng nc-trong-du, cc git dung dch nc b by bi cc phn t CHHBM trong du (cc mixen) (hnh 3). y l mt dung dch trng thi cn bng nhit ng trong sut, ng hng. Do s gii hn v khng gian ca cc phn t CHHBM, s hnh thnh, pht trin cc ht nano b hn ch v to nn cc ht nano rt ng nht. Kch thc ht c th t 4-12 nm vi sai khc khong 0.2-0.3 nm. V d, dodecyl sulfate st, Fe(DS)2, c dng trong phng php vi nh tng to ht nan t tnh vi kch thc c th c iu khin bng nng cht hot ha b mt (CHHBM) l AOT v nhit .
Hnh 3: H nh tng nc trong du v du trong nc. C ch c th ca phn ng xy ra trong h vi nh tng nh sau (hnh 4): Phn ng ha hc to cc cht mong mun s xy ra khi ta ha trn cc h vi nh tng ny li vi nhau. C 2 cch cc phn t cht phn ng gp nhau: Cch th nht: Cc phn t cht phn ng thm qua lp mng cht hot ha b mt ra ngoi v gp nhau. Nhng thc t th t l sn phm to thnh theo cch ny l rt nh,khng ng k. Cch th hai: Khi cc ht vi nh tng ca cc cht phn ng gp nhau, nu c lc tc ng th 2 ht nh (A,B) c th to thnh mt ht ln hn(C). Cc cht phn ng trong 2 ht nh s ha trn, phn ng xy ra trong lng ht ln v sn phm mong mun c to thnh ( y l cc ht magnetite Fe3O4). Cc ht magnetite Fe3O4 sau khi to thnh s b cht hot ha b mt bao ph v ngn cn khng cho pht trin thm v kch thc.
Hnh 4: C ch hot ng ca phng php vi nh tng. Cng bng phng php ny, ngi ta c th ch to ht -xt st bao ph bi mt lp vng trnh -xi ha v tng tnh tng hp sinh hc. y ngi ta dng cetyltrimethylammonium bromide (CTAB) l CHHBM v octane l pha du dung dch phn ng trong pha nc.
mong mun v kt tinh tt. V d, Alivisatos tim FeCup3(Cup: Nnitrosophenylhydroxylamine) trong octylamine vo CHHBM c nhm amino nhit 250 300C thu c cc ht nan tinh th maghemite c kch thc t 4 10 nm. Hyeon to ht nano tinh th maghemite kch thc ng nht 13 nm khng cn dng phng php thy phn m bng cch tim Fe(CO)5 vo trong dung dch c cha CHHBM v mt cht oxi ha nh (trimethylamine oxide). Sun ch to thnh cng ht nan magnetite ng nht kch thc 3 20 nm bng cch cho phn ng st(III) acetylacetonate trong phenyl ether vi s c mt ca ru, oleic acid, v oleylamine nhit 265C. Phng php ny c th to ht nan kch thc 4 nm khi khng c mm kt tinh nhng t kch thc 20 nm th cn phi c mm kt tinh.
Hnh 5: S hnh thnh v pht trin ca l hng trong lng cht lng di tc dng ca sng siu m. Sau nhiu chu k pht trin l hng khng th hp th nng lng sng siu m c na nn b suy sp rt nhanh to thnh cc im nng. Ht nano t tnh da trn oxit st c ch to bng ha siu m. y l phng php rt n gin to ht nan t tnh vi t bo ha rt cao. Mui iron (II) acetate c cho vo trong nc ct hai ln ri cho chiu x siu m vi cng sut khong 200 W/2h trong mi trng bo v. Sng siu m c tc dng di dng xung trnh hin tng qu nhit do siu m to ra. Khi tc dng siu m, trong dung dch s xut hin cc cht c tnh kh v tnh xi ha nh H2, hydrogen peroxide (H2O2). Cc sn phm trung gian nng lng cao c th l HO2 (superoxide), hydro nguyn t, hydroxyl v in t. Cc cht ny s xi ha mui st v bin chng thnh magnetite Fe3O4. Sau khi phn ng xy ra ta thu c ht nan Fe3O4 vi t bo ha c th n 80 emu/g, cao gn bng gi tr ca Fe3O4 dng khi. C ba vng c hnh thnh trong qu trnh chiu x siu m mt cht lng. Vng (a) l vng cht kh nm bn trong l hng. Vng ny c nhit cao v p sut ln lm cho hi nc b nhit phn thnh cc gc t do H v OH. Vng (b) l vng bin gia cht kh v cht lng. Mc d nhit y thp hn vng (a) nhng cng ln phn ng phn hy nhit xy ra. Ngi ta quan st c cc gc hydroxyl t do vng ny. Vng (c) l vng cht lng. y nhit gn bng nhit phng nn xy ra qu trnh ti hp H v OH. Trong ba vng k trn th vng (b) l vng m phn ng ha siu m din ra. Khi chiu x siu m dung dch cha mui iron (II) acetate th xut hin cc phn ng sau: H2O H + OH H + H H2 OH + OH H2O2 Fe(CH3COO)2 Fe2+ + 2(CH3COO)Cht xi ha mnh hydrogen peroxide s xi ha Fe2+ thnh Fe3+ theo phn ng sau: 2Fe2+ + H2O2 2Fe3+ + 2OHCc ion Fe2+ v Fe3+ kt hp vi nhau to thnh magnetite. Tc hnh thnh cc gc hydroxyl c c lng l 25 mM/pht di kh Ar. Bng cch iu khin nhit m chng ti c th to cc ht Fe3O4 vi cc hnh dng khc nhau (hnh 6).
Hnh 8: Nguyn tc nhit phn laser. Nguyn tc ca phng php nhit phn bi hi to ht nano oxit st bt u t mui Fe3+ v mt vi ha cht c vai tr tc nhn kh ion thnh kim loi sau b oxi ha thnh oxit st maghemite. Trong dung dch cn, cc ht maghemite vi kch thc t 5 60 nm c th c hnh thnh vi nhiu hnh dng khc nhau ph thuc vo bn cht ca tin cht cha st ban u. S ca h nhit phn bi hn c cho trong hnh 7. H gm b phn to bi hi dng siu m. Bi hn s c phun vo mt ci l gia nhit phn ng xy ra v ht mn c lm kh trc khi c chuyn n mt h thu cc ht. Vi tin cht l Fe(NO3)3 th ng knh ht mn l 6 nm nhng khi tin cht l FeCl3 th gi tr l 60 nm. Vi st acetylacetonate ht c to ra c kch thc 5 nm v c ng nht rt cao. Nu tin cht l Fe2+ amonium citrate th kt qu l hnh cu rng c ng knh rt ln n 300 nm. V ca cc hnh cu l tp hp cc ht nan nh hn c kch thc t 20 40 nm ph thuc vo nhit ca l. Phng php nhit phn laser c dng ch to ht Si, SiC, Si3N4, Si/C/N, oxit st c kch thc t 5 20 nm. phng php ny lung hi hn hp c cha cht phn ng c nung nng bi laser CO2 v phn ng xy ra do nhit cao (hnh 8). Khi p sut hi v cng sut laser c hn mt gi tr no th ht c hnh thnh v c lc ra ngoi bng kh tr. Ht nano to t phng php ny c kch thc nh, ng nht v hu nh khng kt t. Ngi ta dng phng php ny to ht nan g-Fe2O3 kt tinh tt v c kch thc t 3,5 5 nm. S h nhit phn laser c cho hnh trn.
3. Cc ng dng ht nano t.
3.1. Phn tch v chn lc t bo, AND.
Trong y sinh hc, ngi ta thng xuyn phi tch mt loi thc th sinh hc no ra khi mi trng ca chng lm tng nng khi phn tch hoc cho cc mc ch khc. Phn tch t bo s dng cc ht nan t tnh l mt trong nhng phng php thng c s dng. Qu trnh phn tch c chia lm hai giai on: nh du thc th sinh hc cn nghin cu; v tch cc thc th c nh du ra khi mi trng bng t trng.
Hnh 6: Nguyn tc tch t bo bng t trng. (a) mt nam chm c t bn ngoi ht cc t bo c nh du v loi b cc t bo khng c nh du. (b) nam chm c th t vo mt dng chy c cha t bo cn tch.
Hnh 7: Nguyn tc tch t bo bng t trng s dng bn thanh nam chm to ra mt gradient t trng xuyn tm. S phn tch t bo n gin nht c trnh by hnh 6. Hn hp t bo v cht nh du (ht t tnh bao ph bi mt lp CHHBM) c trn vi nhau cc ln kt ha hc gia cht nh du v t bo xy ra. S dng mt t trng ngoi l mt thanh nam chm vnh cu to ra mt gradient t trng gi cc ht t bo c nh du li. Ngoi lc ht do t trng ngoi, cc t bo cn chu tc dng ca lc y trong lng cht lng. Lc y ny ph thuc vo s khc bit gia khi lng ring ca t bo v nc. Trn thc t lc ny thng c b qua.
Hnh 8: Nguyn l dn thuc dng ht nan t tnh. Mt thanh nam chm bn ngoi rt mnh to ra mt gradient t trng ko cc ht nan t tnh gn vi thuc n v tr mong mun. qu trnh nh thuc din ra lm cho hiu qu s dng thuc c tng ln nhiu ln.
Hnh 9: Nguyn l chc nng ha b mt ca ht nan t tnh c cu trc v/li. Li ca ht l xt st, v l lp silica, cc nhm chc bn ngoi c th l carboxyl, amino, streptavidin, Cc ht nan t tnh thng dng l -xt st (magnetite Fe3O4, maghemite a-Fe2O3) bao ph xung quanh bi mt hp cht cao phn t c tnh tng hp sinh hc nh PVA, detran hoc silica. Cht bao ph c tc dng chc nng ha b mt c th lin kt vi cc phn t khc nh nhm chc carboxyl, biotin, avidin, carbodiimide, (Hnh 9).
3.3. t nhit t
Phng php t cc t bo ung th bng t trng ngoi m khng nh hng n cc t bo bnh thng l mt trong nhng ng dng quan trng khc ca ht nan t tnh. Nguyn tc hot ng l cc ht nan t tnh c kch thc t 20-100 nm c phn tn trong cc m mong mun
sau tc dng mt t trng xoay chiu vi tn s 1,2 MHz bn ngoi ln v cng v tn s lm cho cc ht nan hng ng m to ra nhit nung nng nhng vng xung quanh. Nhit khong 42 C trong khong 30 pht c th git cht cc t bo ung th trong khi cc t bo thng vn an ton (Hnh 10).
Hnh 10: Nghin cu th nghim t nhit t trn th cho thy nhit bn ngoi v bn trong u bu (hai ng trn cng) cao hn nhiu so vi nhit ca nhng vng xung quanh (nhng ng di).
3.6. Chp nh t.
L k thut s dng quan st cu trc men trong lch s, c xy dng ln u tin vo nm 1931 bi F. Bitte. Nguyn l k thut ny l s dng cc cht lng huyn ph c cha cc ht nano xit st (Fe3O4) tm thc ln b mt vt liu t c mi bng rt cn thn. Cc ht st t s bao quanh cc men, v khi s dng knh hin vi quang hc quan st b mt s cho bc tranh v cc men. K thut ny ngy nay hu nh t c s dng do vic hn ch v phn gii, cng nh qu trnh x l mu phc tp, ng thi em li t thng tin trc tip.
[14] K. S. Suslick, The Chemistry of ultrasound trong Encyclopaedia Britannica, Chicago (1994) 138- 155. [15] N. Arul Dhas, C. Paul Raj, A. Gedanken, Preparation of luminescent silicon nanoparticles: a novel sonochemical approach, Chem. Mater. 10 (1998) 3278-3281. [16] M. Sivakumar, A. Towata, K. Yasui, T. Tuziuti, Y. Iida, A new ultrasonic cavitation approach for the synthesis of zinc ferrite nanocrystals, Current Appl. Phys. 6 (2006) 591-593. [17] R. Vijayakumar, Y. Koltypin, I. Felner, A. Gedanken, Sonochemical synthesis and characterization of pure nanometer-sized Fe3O4 particles, Mater. Sci. Engineer. A 286 (2000) 101-105. [18] N. H. Hai, N. H. Luong, N. N. Long, N. Chau, N. D. Phu, S. Theerdhala, A. Gedanken, Proc. Natl. Conf. Solid State Phys. V, Vungtau, Vietnam (2007), 140 (Vietnamese). [19] Pascal C, Pascal J L, Favier F, Elidrissi-Moubtassim M L and Payen C 1999 Chem. Mater. 11 141 [20] Pecharroman C, Gonzalez-Carreno T and Iglesias J E 1995 Phys. Chem. Min. 22 21 [21] Gonzalez-Carreno T, Morales M P, Gracia M and Serna C J 1993 Mater. Lett. 18 151 [22] Veintemillas-Verdaguer S, Morales M P and Serna C J 1998 Mater. Lett. 35 227 [23] Veintemillas-Verdaguer S, Morales M P and Serna C J 2001 Appl. Organomet. Chem. 15 1 [24] Fendler J H 1998 Nanoparticles and Nanostructured Films: Preparation, Characterization and Application (Weinheim: Wiley-VCH) [25] Ulman A 1991 An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly (Boston: Academic) [26] Caruso F, Caruso R A and Mohwald H 1998 Science 282 1111 [27] Caruso F 2001 Adv. Mater. 13 11 [28] Donath E, Sukborukov G B, Caruso F, Davies S A and Mohwald H 1998 Angew. Chem. Int. Ed. 37 2201 [29] Zaitsev V S, Filimonov D S, Presnyakov I A, Gambino R J and Chu B 1999 J. Colloid Interface Sci. 212 49 [30] Gupta P K, Hung T C, Lam F C and Perrier D G 1988 Int. J.Pharmaceutics 43 167 [31] Hassan E E, Parish R C and Gallo J M 1992 Pharm. Res. 9 390 [32] Muller-Schulte D and Brunner D 1995 J. Chromatogr. A 711 53 [33] Alexander I. Petrov, Dmitry V. Volodkin, Gleb B. Sukhorukov, Biotechnol. Prog. 2005, 21, 918-925. [34] Wormuth K 2001 J. Colloid Interface Sci. 241 366 [35] Ulman A 1996 Chem. Rev. 96 1533 [36] Tartaj P, Gonzalez-Carreno T and Serna C J 2001 Adv. Mater. 13 1620. [37] Messing G L, Zhang S and Jayanthi G V 1993 J. Am. Ceram. Soc. 76 2707 [38] Tartaj P, Gonzalez-Carreno T and Serna C J 2002 Langmuir 18 4556 [39] Santra S, Tapec R, Theodoropoulou N, Dobson J, Hebard A and Tan W 2001 Langmuir 17 6000