TIU LUN CNG NGH NANO : FULLERENE46

MC LCI.Tng quan v buckyball3I.1 Lch s ra i3I.2 Cu trc ca mt s fullerenE6I.3 Tnh cht vt l ca C607I.4 Tnh cht ha hc ca fullerene10II.Tng hp fullerene v dn xut13II.1. Phng php tng hp fullerene13II.1.1 Phng php laser13II.1.2. Phng php h quang14II.1.3. Phng php tip cn bng tng hp15II.2. C ch hnh thnh fullerene16II.3. Tng hp cc dn xut fulleren17II.3.1. Dn xut cu trc m18II.3.2. Dn xut vng 3 cnh19II.3.3. Dn xut vng bn20II.3.4. Dn xut vng nm20II.3.5. Dn xut vng su21II.3.6. Dn xut fullerne l21II.3.7. Fullerenes d vng22II.3.8. Cng nhiu cu t22II.3.9. Dn xut halogen23II.3.10. Th i in t HC thm trn C60: C60Ph5H24II.3.11. Fullerene kim loi hu c24II.4. Tnh cht ca cc dn xut fullerene[4]26II.5. Hot tnh sinh hc ca dn xut fullerene:29III.ng dng tim nng ca fullerene31III.1. Quang in hu c (Organic Photovoltaic OPV) - Pin mt tri33III.2. Lu tr hydro35III.3. ng dng quang hc37III.4. Film mng39III.5. Cm bin nn fullernen41III.6. Fullerene lm dy dn phn t41III.7. Fullerene trong dc phm v y hc42III.8. ng dng ca dn xut fulleren dng polyme v polyme h fullerene46III.9. ng dng ca Fullernene endohedral51III.11. Siu dn52III.12. Cc ng dng khc:53IV.Kt lun57

I. Tng quan v buckyballI.1 Lch s ra i[1]Nm 1985, mt nhm nghin cu bao gm Harold Kroto (i hc Sussex, Anh) v Sean O'Brien, Robert Curl, Richard Smalley (i hc Rice, Texas, M) khm ph ra mt phn t cha 60 nguyn t carbon, vit tt l C60.Gio s Kroto l mt nh nghin cu ha hc thin vn.Vo thp nin 70, ng c mt chng trnh nghin cu nhng chui di cc nguyn t carbon trongcc m my bi gia cc v sao. ng lin lc vi nhm ca Curl v Smalley v dng quang ph k laser ca nhm ny m phng iu kin hnh thnh ca cc chui carbon trong cc m my v tr.H khng nhng c th ti to nhng chui carbon m cn tnh c khm ph mt phn t rt bn cha chnh xc 60 nguyn t carbon. S khm ph C60 xoay hng nghin cu ca nhm t tm kim nhng thnh phn ca vt cht ti trong v tr n mt lnh vc hon ton mi l lin h n khoa hc vt liu. Nm 1996, Kroto, Curl v Smalley c gii Nobel Ha hc cho s khm ph ny.Trong vic quyt nh trao gii Nobel, Vin Hn Lm Khoa Hc Thy in qun mt cng lao ca gio s Eiji Osawa. ng lngi u tin tin on s hin hu ca C60. ng tin onC60 vo nm 1970 khi va mi c b nhim Ging Vin ti i Hc Hokkaido. V vit bng ting Nht v ng bi bo co trn tp ch Kagaku (Ha Hc) nm 1970nn khng c cc ng nghip quc t lu n. Mt nm sau ng vit li thnh mt chng cho mt quyn sch gio khoa, cng bng ting Nht. Theo s tnh ton ca ng th nng lng hot ha ca phn ng to ra C60 rt cao. Khi , ng khng th hnh dung c mt cht xc tc no c thh thp nng lng hot ha phn ng c th xy ra. Nhng ng hnh dung c cu trc ca n trong mt ln nhn a con trai ca mnh a gin vi tri bng trong cng vin gn nh. ng cng khng ngh ramt phng tin vt lnh dng laser hoc tia c nng lng cao nh nhm Smalley lm kch hot phn ng. Hn na, thi im ng mi va lm ging vin nn cn phi to mt du n no trong phn khoa. ng cm thy vic tng hpC60 qu nhiu kh khn nn nh chn mt hng nghin cu khc. C mt iu lm cho ng c an i phn nol trong bi din vn nhn gii NobelKroto, Curl v Smalley cp n thnh qu tin phong ca ng.

Hnh 1: Ta bi bo co "Cht thm siu ng" (Super-aromaticity)

Sau khi nhn din C60 t quang ph hp th Kroto, Curl v Smalley bt u to m hnh cho cu trc ca C60. Trong qu trnh ny cc ng nhanh chng nhn ra rng cc nguyn t carbon khng th spphng theo kiu lc gic t ong ca than ch nhng c th sp xp thnhmt qu cu trn trong hnh lc gic xen k vi hnh ng gic ging nh qu bng (Hnh3). Phn t mi ny c t tn l buckminster fullerene theo tn lt v h ca kin trc s Richard Buckminster Fuller. ng Fuller l ngi sng to ra cu trc mi vm hnh cu vi dnglc gic (Hnh2). Cho vn tt ngi ta thng gi C60 l fullerene hay l bucky ball.

Hnh 2: Kin trc s Richard Buckminster Fullerv mi vm hnh cu vi m dnglc gicS dng tia laser lm bc hi thanh graphite trong mt bu kh quyn helium, cc tc gi thu c cc phn t dng lng gm 60 nguyn t carbon (C60) ni vi nhau bi lin kt n v i to thnh mt qu cu rng vi 12 mt ng gic v 20 mt lc gic - mt thit k tng t nh mt qu bng . Fullerene l dng th hnh th t ca carbon (ngoi than ch, v nh hnh v kim cng) hay theo 1 s ti liu khc l dng th hnh th by ca carbon (cng vi hai th hnh kim cng, hai hnh thc graphite, chaoit (1968), v carbon (IV)(1972))[2].

Hnh 3: C60

Hnh 4:C540

Hnh 5: Sir Harold W.Kroto

Hnh 6: Cu trc a lp ca than ch

Hnh 7: Cu trc kim cng

Hnh 8: Mt buckyball di hn dng nh bng bu dc C72

Cc fullerene, c bit l nhng qu cu C60 rt i xng, c mt v p sang trng kch thch tr tng tng ca cc nh khoa hc ln ngi bnh thng, chng lin kt khoa hc thm m, kin trc, ton hc, k thut v ngh thut th gic. Khm ph ca chng dn n mt s hiu bit hon ton mi v hnh vi ca vt liu tm v n m ra mt chng hon ton mi ca khoa hc nano, "ha hc mi" ca cc h thng phc tp quy m nguyn t th hin hnh vi vt liu tin tin. T nm 1985 n nm 1990, mt lot cc nghin cu ch ra rng C60 v C70 cng thc s c bit n nh v cung cp bng chng thuyt phc cho xut cu trc lng. Ngoi ra, bng chng thu c cho s tn ti ca cc hp cht nh siu bn khc, chng hn nh C28, C36, C50 v bng chng thc nghim c cung cp cho cc c s "endohedral", trong mt nguyn t b mc kt bn trong lng. Cc th nghim cho thy rng kch thc ca mt nguyn t c ng gi xc nh kch thc ca cc th lng xung quanh nh nht. Lch s fullerene lu i hay non tr ty vo hai cch nhn khc nhau. Nghin cu fullerene tht ra rt ngn ch trn 30 nm k t ngy ph khi ca Curl v Smalley cho bit s hin din ca C60 v C70, nhngs hin hu ca fullerenecn sm hn s xut hin ca loi ngi. N c trong nhng m my bi trong v tr, m than, b hng t nhng ngn nn lung linhhoc nhng ni khim tn hn nh l si than, l ni... Ngi ta khng tm c C60 v hm lng rt nh v thng b than v nh hnh ph lp.I.2 Cu trc ca mt s fullerene[3-5]Mt s lng v hn ca fullerene cu c cho l c kh nng tn ti vi s lng carbon t 20 n hng trm nguyn t. Tt c fullerene bao gm 12 mt ng gic v cn li l mt hnh lc gic. Cc mt ng gic nm trn cc nh ca khi 20 mt (icosahedron) v do 2 mt ng gic khng bao gi nm cnh nhau. Tng qut, mt fullerene C-n s c 12 mt ng gic v n/2-10 hnh lc gic; do , C-60 fullerene c 12 mt ng gic v 20 mt hnh lc gic, nh nht l C20 vi cu trc gm 12 mt ng gic v khng c mt lc gic.Nguyn t cacbon trong fullenrene c lai ha gn ging sp2 v cc obital s dng lin kt sigma vi 3 nguyn t cacbon ln cn l lai ha ca obital 2s v hai obitan 2p (2px v 2py). Obital 2p cn li tng ng vi lin kt pi. Gc gia trc p v Vector lin kt C-C, , l 101,6o. Hnh bt hoc lm mi cacbon sp2 to ra mt s cng thng vo cc phn t.Xc nh cu trc tinh th x-ray trn C60 v mt s dn xut ca n xc minh s tn ti ca hai loi lin kt khc nhau: lin kt ngn hoc lin kt vng 6,6, chia s bi hai hnh lc gic lin k (1.38A) v lin kt di, hay lin kt vng 5,6, l giao ca ng gic v mt hnh lc gic (khong 1,45A). Chiu di lin kt C-C trung bnh theo NMR l 1.44A). ng knh phn t C60 khong 7.09A. Khi ph c s dng rng ri nghin cu fullerene.

Hnh 9:Ph hng ngoi ca C60Hnh 10: Ph C13 NMR ca C60

C60 ch c bn peak IR, do tnh i xng 20 mt ca n.Hnh 11: Ph UV.kh kin tinh khit C60Hnh 12: Khi ph cho thy cc peak fullerene cao hn hin din trong mui carbon

I.3 Tnh cht vt l ca C60[2]:Phn t C60 k nc mnh, tan hn ch trong mt s dung mi hu c, hon ton khng tan trong nc.Dung mi tan (mg/mL)

Nc--

hexane40

Dioxane41

cyclohexane51

carbon tetrachloride447

Benzene1,440

toluene2,150

carbon disulfide5,160

Bng 1: tan ca C60 trong mt s dung mi

Hnh 13:T tri sang phi: C60, C70, C76, C78, C84 trong dung dch

Dung dch ca fullerene tinh khit c mu tm. Dung dch ca C70 mu nu . Cc fullerene cao hn C76 n C84 c mt lot cc mu sc. C76 c hai ng phn quang hc, trong khi fullerene cao khc c nhiu ng phn cu trc. Fullerene l dng th hnh duy nht ca carbon c th c ha tan trong dung mi ph bin nhit phng.Mt s thng s vt l: T trng: 1.65 g/cm3 Nhit hnh thnh tiu chun: 9.08 kcal/mol Ch s khc x: 2.2 (600nm) im si: thng hoa ti 800K in tr sut: 1014 ohms/m Mt hi: N / A Dng tinh th hnh lc gic khi p sut hi: 5 x 10-6 torr nhit phng, 8 x 10-4 torr 800KTnh cht cm quan: Mui Buckyball: bt mu en rt mn Fullerite: Nu / bt mu en C60: en rn Mi: Khng miHnh 14: Ph HPLC cho thy fullerenes tm thy trong mui than

Fullerene l cc phn t cc k mnh m, c kh nng chng li p lc tuyt vi, chng phc hi tr li hnh dng ban u sau khi chu hn 3.000 atmosphere. L thuyt tnh ton cho thy rng mt phn t C60 n c hiu qu module trn 668 GPa khi nn n 75% kch thc ca n. Tnh cht ny khin fullerene tr thnh cng hn so vi thp v kim cng, c mun ln lt l 160 GPa v 442 Gpa. Mt th nghim th v cho thy fullerene c th chu c va chm vi tc ln ti 15.000 dm/h vi thp chng g, ch vng qua li v gi hnh dng ca chng. Th nghim ny cho thy bn cao ca cc phn t[5].Electron pi di ng trong fullerene cung cp cho phn ng quang hc phi tuyn (nonlinear optic) c bit ln. Quang hc phi tuyn (NLO) l chi nhnh ca quang hc m t hnh vi ca nh sng trong mi trng phi tuyn, c ngha l, mi trng trong s phn cc lng cc P phn ng phi tuyn n cc in trng ca nh sng. Phi tuyn ny thng ch quan st thy nhng cng nh sng rt cao (gi tr ca in trng c th so vi in trng gia cc nguyn t, thng 108V/m) nh nhng nh sng c cung cp bi laser. Vt qu gii hn Schwinger, chn khng t n c d kin s tr thnh phi tuyn. Trong quang hc phi tuyn, cc nguyn tc chng cht khng cn ng na. Fullerene th hin ha hn c bit l trong gii hn quang (optical limit). Ngoi ra, s chuyn ca cc electron t cc nguyn t i km n cc fullerene nng cao hiu ng quang hc phi tuyn bc ba v ln so vi fullerene rng[5].

Hnh 15:C70Hnh 16: Ph hng ngoi ca C70Hnh 17: ph t ngoi/kh kin ca C70

Hnh 18: ph C13 NMR ca C70Hnh 19: C76Hnh 20:C84

Hnh 21: Cu trc ha hc FullereneHnh 22: Cu trc ca lp graphene

I.4 Tnh cht ha hc ca fullerene[2-4]Fullerene c tnh cht ha hc phong ph v phc tp vi hn 15.000 bi bo nghin cu trong vng 15 nm u tin khm ph ra. C60 bn vi acid/base yu, tc nhn oxi ha yu, vi tc nhn kh yu v cc iu kin phn ng khc bao gm iu kin ni peptide. Mi nguyn t carbon c gn vi ba nguyn t khc v c lai ha sp2. Cc phn t C60 c hai chiu di lin kt lin kt vng 6: 6 c th c coi l "lin kt i" v ngn hn lin kt 6: 5. C60 c xu hng trnh vic c lin kt i trong vng ng gic lm cho ngho electron linh ng v kt qu trong thc t l C60 khng phi l "superaromatic". C60 th hin rt ging mt alken thiu electron v sn sng phn ng vi cht giu electron, nhng cng c th i khi th hin theo mt cch tng t nh cc vng thm.C60 phn ng d dng vi nucleophile v l cu t 2p trong phn ng cng vng. Phn ln cc cht phn ng s tn cng nt giao vng 6,6 ca C60, ni c mt electron cao hn. S cng thm vo lin kt 5,6 c bo co ch l sp xp li sau mt cuc tn cng nt giao 6,6.V ging alken thiu in t, fulleren phn ng d dng vi cc phn t giu electron v tham gia vo nhiu phn ng ha hc ca alken (bao gm oxy ha-kh, cng i nhn, cng i in t, phn ng Diels-Alder v Friedel-Craft alkyl ha). Phn ng cng vng tiu biu: Diels-Alder Cng vng 1,3-lng cc Cng Carbene Cyclopropan ha BingelPhn ng gc t do: C60 ln n 20 gc t doCc b mt C60 cha 20 hnh lc gic v 12 ng gic, tt c cc vng c hp nht, tt c cc lin kt i lin hp c. Do nhu cu hnh hc ca lng cu nn tt c cc lin kt i C60 i lch khi mt phng. S to hnh chp ca cc nguyn t carbon lai ha sp2 em li s d tha ca sc cng ln C60, c trch nhim nng cao hot tnh phn ng ca fullerene. S gim sc cng trong thc t lin quan n s thay i ca lai ha t sp2 thnh sp3 i km vi hu ht phn ng ha hc.Khong cch HOMO-LUMO ca fullerene l 1,68 eV. Do cc LUMO nm mc nng lng thp, fullerene kh mt cch d dng, lm cho fullerene thnh mt tc nhn oxy ha tt. Fullerene khng n nh nhit cao. Qu trnh phn hy nhanh trong s c mt ca oxy c th c quan st thy khong 830K.C60 v C70 c tnh cht tng t nhau, vi s oxi ha C60(6-) v C70(6-) c quan st. Tuy nhin qu trnh oxy ha ca C60 v C70 khng th o ngc. Th kh c hai fullerene l ~1.0V (Fc/Fc+), cho thy chng c tnh nhn electron. C76 th hin c tnh cht cho/nhn electron.Cc phn t C60 sn sng nhn v cho in t, mt hnh vi c th cho thy cc ng dng vo cc thit b in t trong pin tin tin. Cc phn t d dng b sung thm cc nguyn t ca hydro v cc halogen. Cc halogen c th c thay th bi cc nhm khc, chng hn nh phenyl, v vy m ra mt lot cc dn xut fullerene mi. c bit th v trong ha hc fullerene l loi endohedral trong mt nguyn t kim loi (M) b mc kt bn trong mt ci lng fullerene. Cc dn xut (cng thc M @ C60) c nghin cu rng ri. Kim loi kim v kim loi kim th cng nh h lanthan c th b mc kt do bc hi a than ch hoc que ngm tm vi cc kim loi c la chn. He cng c th b mc kt bng cch nung nng C60 trong hi helium di p lc.Phn t fullerene c pht hin mang c tnh vi t bo khi tip xc nh sng. Hnh 23 cho ta thy c ch:

Hnh 23: C ch ca fulleren khi tip xc nh sngFullerene (C60) t trng thi c bn b kch thch bi bc x nh sng n mt trng thi kch thch v chuyn i sang cht tui th ngn, 1C60. 1C60 ny chuyn ha thnh cht tui th di, 3C60 bi qua intersystem crossing (ISC). Trong s hin din ca oxy, 3C60 c th truyn nng lng ca mnh cho O2 v quay tr li trng thi cn bng, to singlet oxygen, 1O2 m c bit n nh l mt cht c t bo hoc cht phn ng i vi DNA. Chuyn nhng electron 3C60 c th c kh n gc t do anion fullerene, C60.- v C60.- c th truyn mt electron sn xut anion superoxide trit , O2.- c bit n nh l cht phn ng vi DNA.II. Tng hp fullerene v dn xutII.1. Phng php tng hp fullereneII.1.1 Phng php laserPhng php u tin sn xut fullerene s dng s bay hi laser carbon trong kh tr, nhng ch sn xut mt lng nh ca fullerene. Laser bay hi cng c s dng cho sn xut fullerene. Trong mt thit b tiu biu mt xung laser hot ng 532 nm v cng 250 mJ c s dng nh l ngun laser v cc bia graphite c gi trong mt l 1200C.

Hnh 24: S bn v mt ct ngang ca thit b phun laser bay hi iu ch C60II.1.2. Phng php h quangNm 1990, Kratschmer v Huffmann pht trin mt phng php phng in h quang sn xut qui m ln, c gi l phng php Krtschmer-Huffman (KH). H pht hin ra rng cc thanh in tr carbon b nng trong bu kh quyn helium to vi gram fullerene ln trong mui carbon. Phng php ny bao gm in cc graphite tip xc vi h quang qua in xoay chiu hoc mt chiu i qua chng trong mt bu khng kh helium khong 200 torr. Cc graphite bc hi to thnh dng b hng, c ha tan trong mt dung mi khng phn cc (vd toluen). Cc dung mi c loi b bng cch s dng mt thit b bay hi quay, li mt hn hp rn ch yu l C60 vi mt lng nh fullerene ln hn. C60 tinh khit thu c bng sc k lng. Hn hp ny c ha tan trong toluen v bm qua mt ct than hot tnh trn vi silica gel. Cc dung dch C60 mu tm ra u tin, tip theo l dung dch mu C70. Cc dung dch mu sc khc nhau c thu thp mt cch ring bit v toluene loi b bng cch s dng bay hi quay. Hin nay, vi p lc v tc dng ti u ca helium v cng dng in dn n hiu sut ln n 70% ca C60 v 15% C70 vi phng php ny. Ngoi ra, fullerenes cng c th c sn xut trong lin quan n tro t, v d, t benzen v acetylene, mc d sn lng thp.

Hnh 25: M phng b my Kratcshmer-Huffmann nh c s dng ti i hc Widener

Hnh 26: Minh ha phng php K-HII.1.3. Phng php tip cn bng tng hp Fullerene t s bay hi ca than ch hoc bng cch t chy cc hydrocarbon rt hiu qu v cnh tranh. Tuy nhin, phng php tip cn bng tng hp cng rt hp dn bi v (a) fullerene c th c th c thc hin mt cch chn lc v ring bit(b) fullerene endohedral mi c th c hnh thnh(c) fullerene d t(d) cm fullerene bin tnh khc c th c to ra bng cch s dng phng php tng hp lin quan.Hnh 27: Chuyn ha cyclophane thnh C60 trong pha kh trong ph khi laser gii hpHnh 28: Tng hp t circumtrindene, to thnh 60% C60Hnh 29: Tng hp C60 bi cyclodehydrogenation ca polyarene

II.2. C ch hnh thnh fullereneMc d c nhiu c ch c trnh by, ch c c ch con ng ng gic theo gio s Richard Smalley c th gii thch cho hiu sut cao ca C60. Ti thi im ny ch c mt c ch xut hin ph hp vi sn lng ca C60 cao 30-40%. N c gi l Con ng ca mt ng gic. Theo quan im ny, nng sut cao do nhng b ni tip nhau trong mt khu vc nng cho php cc b pht trin qua con ng nng lng ti thiu: mt ni tm graphene (a) c to thnh ch nhng mt ng gic v lc gic, (b) c nhiu hnh ng gic nht c th, trong khi (c) cc cu trc trnh hai ng gic l lin k. Nu cc cu trc quy tc ng gic thc s l nhng hnh thc nng lng thp nht cho bt k mng li carbon m, th ngi ta c th d dng tng tng rng tng hp nng sut cao ca C60 c th thc hin c. V nguyn tc, tt c iu cn phi lm l iu chnh cc iu kin ca cm carbon tng trng nh vy m mi cm m c nhiu thi gian pht trin theo quay lut cu trc ng gic a thch ca n trc khi n pht trin hn na. Con ng thng qua ng hc ny gi l con ng ca mt ng gic v to thnh mt c ch ca tm graphene t lp rp dn n C60 vi nng sut rt cao.iu ny i hi nhit tng trng cm cao pht trin cc cu trc m khi chng trng thnh v th chng i theo con ng ng gic, nhng m nhit khng qu cao cho php sp xp li rng v gn kt ca cc ro cn hot tnh cao cn thit chuyn i cu trc t ng gic m n fullerene kn.Trong th nghim ca Krtschmer-Huffman (KH), cc gc carbon c sn xut n gin bng cch bay hi chm ca b mt ca mt thanh graphite c gia nhit. y, mt hi carbon thp hn so vi bay hi bi xung laser, do tc b li cng nh vy. Quan trng nht, tc lm mt ca hi ngng t carbon chm hn nhiu trong phng php KH. Bng cch iu chnh p sut kh helium m xung quanh cc thanh graphite bc hi, phng php ny t nht c th kim sot th tc lm mt v tc to b. Ti p sut qu thp cc gc carbon di chuyn xa khi vng nng quanh que lm nng v qu lnh khi chng pht trin n cc vng ca C60. Nhng ch khi p sut heli ng, cc b trong phm vi kch thc ti hn xy ra va ng khong cch t ngun nng l nhit ti u cho cc cm pht trin theo con ng ca Mt ng gic.Sau khi phng php KH c gii thiu, i hc Rice pht hin h quang xoay chiu hay 1 chiu n gin s sn xut C60 v cc fullerenes khc v sn lng cng tt v by gi l phng php s dng thng mi. Mc d c ch bay hi ca mt h quang carbon khc nhau r rt vi mt thanh carbon lm nng din tr (v n lin quan n mt plasma), p lc helium ti u cho hnh thnh C60 c tm thy l rt ging nhau trong tng trng hp. Bng cch iu chnh p sut kh helium m, c th iu khin tc ca vic di c ca hi carbon t que than ch nng v do iu khin (t nht l th s) nhit nh hng v mt gc t do carbon trong khu vc ni cc cm trong phm vi kch thc gn C60 c hnh thnh.C ch ca ng ng gic ch l mt trong rt nhiu c ch m fullerene c th hnh thnh, nhng n c th chim mt thc t ng ch nht nht ca hnh thnh fullerene: nng sut C60 tng th c th cao n 40% ca tt c cc carbon bc hi. ng Ng gic gii thch iu ny nh l mt h qu ca ti luyn cc tm graphene m ra cho cu trc m ti u (do cc quy lut ng gic) vi mt tc nhanh hn so vi tc tng trng, trong khi trnh sp xp li mt fullerene kn trc khi t kch thc ca C60. y l mt trng hp chn cc iu kin phn ng c li cho mt sn phm c th. II.3. Tng hp cc dn xut fulleren[4]II.3.1. Dn xut cu trc mSn phm cng c th thu c bng cch hydro ha cn thn (Nu = E = H), hoc bng cch thm mt tc nhn nucleophin theo sau bi dp tt bng axit hoc mt electrophile (S 1).Thng thng, phn ng cng 1,2 c quan st, nhng cng 1,4 c bo co trong mt vi trng hp c cn tr. Nucleophile c thc hin thnh cng hon ton bao gm cc thuc th Grignard, cc dn xut organolithium, ion cyanide,.... Mt trng hp minh ha cc tin ch ca phng php ny sn xut vt liu th v c minh ha trong trong S 1. Cyanide cng vo C60, tip theo l dp tt vi toluene-p-sulfonyl cyanide, dn n s tng hp ca mt dinitrile phi sinh 1 (Nu = E = CN). 1 v nhng monocyano-dihydrofullerene khc th hin cc thuc tnh th v, cho php tinh chnh cc kh nng chp nhn electron ca cyanohydrofullerene.

Hnh 30: Hnh dng hnh hc c xy dng trn mt khp ni 6,6 vng C60 : (a) m, (b) vng ba, (c) vng bn, (d) vng nm v (e) vng su

Hnh 31: S 1II.3.2. Dn xut vng 3 cnhLoi ny i din cho mt trong nhng lp hp dn nht v nghin cu k lng nht ca fullerene chc nng ha. Vic b sung cc dn xut diazomethane n C60, tin phong bi nhm Wudl c th dn n hai cu trc khc nhau, thng c gi l fulleroid 3 v methanofullerene 4.

Bc u tin ca phn ng l mt cng vng 1,3-lng cc ca diazomethane n C60, to ra mt dn xut pyrazoline 2. y nit ra thng dn n mt hn hp ca fulleroid v methanofullerene. S chuyn ha fulleroid thnh methanofullerene c th t c (trong hu ht cc trng hp, tr R= R= H60) bng nhit, in ha hoc quang ha. N cng c th l xc tc axit. Mt lot cc diaryl, arylalkyl v dialkyl fulleroid v methanofullerene c tng hp cho n nay, cung cp nguyn liu cho cc ng dng tim nng trong nhiu lnh vc.Vng ba hp nht trn khp ni 6,6 ca C60 c th c sn xut in ha sch (khng c hnh thnh fulleroid) hoc bng cch thm nucleophile, diazirine, carbene, sulfonium ylide.Cng azid vo C60 theo sau cht ch vi qu trnh phn ng ca cc hp cht diazo. Trong trng hp ny, cc dn xut triazoline c th c c lp v xc nh, m sau khi y nit, dn n azafulleroid. Nu nitrene c to ra thay th, azamethano fullerene c to thnh.Th v lu rng, trong nhiu gia nh ca organofullerene, fulleroid v azafulleroid l dn xut duy nht duy tr cu hnh electron 60p in hnh ca C60.II.3.3. Dn xut vng bnCc dn xut Cyclobutanofullerene thng thu c bng cch cng vng (2 + 2). Cng Benzyne c bo co u tin, theo sau bi s cng cc anken ngho electron, alkene giu electron v alkyne. Cng vng (2 + 2 + 2) ca quadricyclane n C60 to dn xut norbornene c s dng cho tng hp polymer.II.3.4. Dn xut vng nmChng thng c tng hp bi cng vng (3 + 2). Mt lot cc h cacbon hoc d vng c bo co, trong bao gm cc dn xut cyclopentane, pyrrolidine, isoxazoline, pyrazoline, furan....Vic cng ylide azomethine vi C60 to ra fulleropyrrolidine ang tr nn ngy cng ph bin. L do cho s thnh cng nh vy c l l do cch tip cn n gin, vt liu bt u thng l c sn thng mi hoc d dng tng hp v mt sn phm duy nht ca cng n qua mt khp ni 6.6 ca fullerene thu c (S 2).

Hnh 32: S 2II.3.5. Dn xut vng suCng vng c in Diels - Alder (4 + 2) vi C60 sn xut vng su hp nht vi khp ni 6,6. y cng l mt phn ng rt ph bin, s dng bi nhiu nhm, trong to mt lot cc chc nng ha fullerene.II.3.6. Dn xut fullerne lK t khi pht hin fullerene, tng v by cc nguyn t, phn t hay ion bn trong lng carbon cun ht cc cng ng khoa hc. H tin rng vt liu mi vi nhng tnh cht c bit c th c sn xut. Trong khi , mt s fullerene c cha cc kim loi chuyn tip bn trong c phn lp, vic tng hp vi s lng ln ca khi cha s i hi bin tnh ha hc ca C60 nh vy m mt l c m ra trn b mt fullerene bng cch ph v mt hoc nhiu lin kt i. Sau , cc nguyn t, phn t hoc ion phi c buc bn trong lng v b mc kt bng cch khi phc lin kt carbon - carbon. Khi nim rt n gin nhng vic m mt l trn lng fullerene rt kh khn. Cc l u tin to c rch bng oxy ha nh. Tuy nhin mu c tng hp trn mt quy m phn tch v ch c c trng bi ph IR. Mt l vng mi mt cnh c to ra trn cc b mt fullerene bng cng i la chn vng ca azide. Mt kt qu rt th v c tit l thi gian gn y bi Hirsch v cng tc vin, ngi bo co cc v d u tin ca bin tnh ha hc ca fullerene cho php tng hp cc ng phn ha tr m v ng vi cc m hnh b sung tng t. H pht hin ra rng sn phm cng i 5 v 6 hnh thnh bng cch cng azide vi C60 c cu trc khc nhau, ty thuc vo cc nhm th trn nguyn t nit. Sn phm cng khng th 5 b kha dng vng kn, trong khi mt chc nng carbamate lm pht sinh cc hnh thc m, trong c mt l tng i ln.

Saunders v cng tc vin chng minh rng nhit cao (650C) v p sut rt cao (3000 atm) cc kh tr helium, neon, argon, krypton v xenon c th a vo bn trong lng ti mt trong mi 1000 phn t C60. Ph v lin kt tm thi ca lng c xut gii thch qu trnh. V nhng l do hin nhin phng php ny khng th c m rng mt cch d dng vi nhng khch khc tr kh tr. Ngoi ra, Saunders cnh bo rng tng hp ha hc p sut mi trng xung quanh c th khng thnh cng do cn lng nh th tch t do bn trong khi cu fullerene.II.3.7. Fullerenes d vngMt mc tiu khc ca ha hc fullerene lin quan n vic c th thay th mt hay nhiu nguyn t carbon ca lng vi nguyn t d t. Thay th ny dn n fullerene d vng, trong c th c nhng tnh cht khc fullerene. Nguyn t d t ph bin nht l nit v C60 tng ng c phn lp vi s lng ln nh dimer ca n l (C59N)2. Cc tnh cht ha hc v vt l ca cc hp cht mi l i tng ca nhng dng nghin cu mnh m.II.3.8. Cng nhiu cu tC60 s hu 30 ng lng lin kt i, tt c u c hot tnh tng ng. Thng thng, vic cng thm mt tc nhn nucleophin cho mt lin kt 6,6 ca C60 trong mt s lng cn bng ha hc dn n mt hn hp phc tp c cha mt sn phm ca cng n cng vi mt vi sn phm cng nhiu hn. Thng thng, cc sn phm cng n c tch bng sc k v sn phm nhiu cng b i. iu ny l bi v mt hn hp ca sn phm cng kp (t mt cht phn ng i xng) c th cha ln n tm ng phn v tr khc nhau, vi s lng cc ng phn c th tng vi s lng phn ng cng. ng phn bn trong mi gia nh ca sn phm cng (cng n, cng kp, cng 3) c xu hng cng c tnh sc k v iu ny lm cho s phn ly thnh mt hot ng rt phc tp. V vy, iu kin cng khc thng c ti u ha cho nng sut ti a ca sn phm cng n.Gn y, ha hc ca cng nhiu vo li fullerene tr thnh mt vn c bn trong thit k ca cc dn xut C60 hu ch v mt vi nhm nghin cu a ra nhng thch thc ca c lp v c trng sn phm cng kp cng nh sn phm cng cao hn. Nghin cu ca polyaddition c thc hin bng cch s dng osmylation, g2-kim loi phc, hydro ha, vng cyclopropan ha, cng azide, cng vng (4 + 2), cng vng (3 + 2), cng vng azomethine ylide, silylation, epoxidation v cng amin.c bit, nhm Hirsch v nhm Diederich tham gia vo mt nghin cu c h thng nhm xc nh cc yu t chi phi regiochemistry ca nhng phn ng cng v kim sot phn ng cng nhiu. Nhm ngi c, sau khi c lp v xc nh c tnh ca mi sn phm cng kp hnh thnh trong phn ng cng c s xc tc ca bromomalonate, i n kt lun rng vic b sung mt tc nhn nucleophin th hai khng xy ra mt cch ngu nhin m c iu khin bi cc orbital phn t bin gii ca fullerene c 1 cha nng ha. Hn na, trong mt bc i quyt nh i vi s tng hp ca sn phm cng hexakis, mt nhm tng t thc hin cng thun nghch 9,10-dimethyl anthracene sn xut cc sn phm cng i xng Th - hexakis ca cyclopropanation ca C60 vi mt m hnh cng bt din vi hiu sut ng kinh ngc 48%. Mt khc, cc chin lc c s dng bi cc nhm ETH c cc chc nng ha trc tip gii hn ca C60, trong sn xut sn phm cng ring bit bt ngun bi cng xch o. Cch tip cn ny cho php cc nhm Thy S t c kt qu xut sc, nh hai i din c kh nng ha tan ca mt lp mi ca dng th hnh carbon, C195 v C260. Mt trng hp duy nht ca kim sot theo ha hc topo s hai chc nng ha fullerene c bo co gn y. Trong trng thi rn, khi un nng 180C trong 10 pht, cc tinh th ca sn phm cng n C60 v anthracene pht trin ti sn phm cng i i cc theo mt cch nh lng.Cc dn xut Polyhydroxylate C60, fullerenol C60(OH)10-12, c th thu c bng nhiu phng php khc nhau. Cc nhm hydroxy c phn phi ngu nhin trn b mt fullerene, to ra hn hp cc cu trc ng phn, nhng cung cp mt mt cao ca cc tm phn ng hu ch cho cc ng dng thc t.Mc d cha th kim sot hon ton cc phn ng cng ha hc cc fullerene, nhng kt qu ng khch l c bo co cho n nay m ng cho nhng hy vng rng trong tng lai cc fullerene v c bit l C60 c th c s dng nh l cc khi xy dng trong xy dng cm phn t rt phc tp.II.3.9. Dn xut halogenNh ni trn, fullerene hnh x nh alkene thiu electron v phn ng vi cc cht giu electron, chng hn nh cc halogen. Hnh thnh cc C60Br24 bi phn ng ca C60 rn vi brom lng nn cht mt 5-8 ngy, nhng c mt phng php mi c pht trin ti i hc Widener, lm gim thi gian phn ng cn khong mt gi.

Hnh 33: C60Br24

Thc nghim: C60 (50mg) c t trong mt bnh cha kn vi brm lng nn cht (5ml) v dy st ln (khong 1g), v khuy nhit phng trong 1h. Br lng tha c ly ra bng cch bc hi chn khng v cht rn thu c x l vi methanol loi b FeBr3 hnh thnh trong qu trnh phn ng. Cht rn cn li sau c lc v ra sch vi methanol.C ch: C ch c cho l tng t nh ca th i in t ca Hydrocarbon thm, tc l s hnh thnh ti ch ca FeBr3, mt xc tc axit Lewis cc phn ng bng cch phn cc phn t Br2 tn cng lc in t.II.3.10. Th i in t HC thm trn C60: C60Ph5HCu trc ca C60Ph5H, hnh thnh qua th i in t HC thm. Phn ng ca C60Cl6 vi benzene/FeCl3 to thnh C60Ph5Cl ri d dng kh thnh C60Ph5H, sn phm chnh ca phn ng C60 vi Br2/ FeCl3/benzen. C hai hp cht c c trng bi quang ph NMR.

Hnh 34: M hnh khng gian ca C60Ph5H (tri) v tinh th ca C60Ph5H (phi)

II.3.11. Fullerene kim loi hu cCc hp cht ca fullerene c th c phn loi theo hai hng mc khc nhau: Exohedral (bn trong lng) v Endohedral (bn ngoi lng). V d ca exohedral v cc kim loi nh La trong lng C82 v v d endohedral bao gm cc phc kim loi chuyn tip nh vi Ir, cng nh phn hon ton lin kt hu c vi lng fullerene.a. Hp cht Endohedral

Hnh 35:La@C82

Khi C60 c pht hin u tin, cc th nghim mi c nhanh chng a ra kim tra gi thuyt C60 nh l mt cu trc lng kn. Cu trc C60 l rng, c ch cho mt hoc nhiu nguyn t khc, nhiu n lc c thc hin nht vo mt nguyn t kim loi. Mt tm graphite c ngm vi dung dch mui kim loi (lanthanum chloride, LaCl3) v b bc hi-ngng t. Phn tch quang ph khi lng ca cc cm c hnh thnh cho thy s hin din ca C60La+. iu ny cng c tng rng cc nguyn t kim loi c "bt" bn trong cc cu trc lng. Ci gi l th nghim "thu nh lng" sau c a ra, theo cc ion ca mt kch thc (hoc kch thc tng t) b bt trong mt by t v phi chu mt xung laser. Cc xung laser lm cho lng carbon thu nh bng 2 nguyn t carbon mt thi gian, cho n khi p lc trn cc nguyn t kim loi b mc kt l qu ln. Lng carbon khi ph hp chnh xc xung quanh nguyn t kim loi. V d, i vi C60Cs+ kch thc ny l ti C48Cs+ v i vi C60K+ n l C44K+. Tin b quan trng gn y c nh du bi s c lp thnh cng v thanh lc ca Sc@C82, Y@C82, La@ C82, Gd@C82, La2@C80 v Sc2@C84 s lng ln. Cc thuc tnh ca fullerene rng c bin i khi doping endohedral kim loi. Nhm Akasaka lm r cc cu trc in t v tnh cht ca metallofullerene endohedral da trn cc tnh ton l thuyt v thc hin cc chc nng ha exohedral u metallofullerene vi hp cht organosilicon c th hot ng nh mt my d c hc lm r cc thnh phn in t v ha hc ca fullerene. b. Hp cht Exohedral (C60 nh mt ligand)Nhiu hp cht exohedral c tng hp, chng hn nh cc phc Pd v Ir hin th di y. Cc phi t fullerene trong nhng trng hp ny ch hot ng trong mt cch tng t nh olefin.Hnh 36:Fullerene-bis(PPh3)-palladiumHnh 37:Fullerene-bis(benzoyloxybenzoyl (diphenyl) phospine)-chloro-carbonyl-iridium

Hn na, nhng dn xut exohedral thnh cng ca metallofullerene endohedral m ng cho mt lot cc thc th ha hc mi c tnh nng mi l, lm phong ph thm cc cht ha hc ca metallofullerene.II.4. Tnh cht ca cc dn xut fullerene[4]II.4.1. Tnh cht in haT nhng ngy u ca ngnh ha hc chc nng ha, in ha ca cc dn xut fullerene c nghin cu c h thng bi cc nhm Wudl ti i hc California ti Santa Barbara. Trong thc t, mt tnh nng ni bt ca C60, c th hin bng voltammetry cyclic* l trong dung dch fullerene c th nhn thun nghch ln n su electron. Nhm UCSB thy rng c hai fulleroid v methanofullerene c bn gi nguyn tnh cht in t ca C60. c tnh tng t c quan st thy i vi hu ht cc dn xut ca C60 m voltammogram cyclic thng c c trng bi mt s chuyn nh sang cc gi tr m hn ca th kh. iu ny c cho l do s bo ha ca mt lin kt i trong C60 lm mt mt phn ca h lin hp. Do nh hng ny, ti hu ht 5 peak kh ca nhm chc C60 trong cc dn xut fullerene c pht hin cho n nay nm trong vng th tip cn c.*Voltammetry Cyclic (CV) l mt k thut phn tch in (electroanalytical) quan trng v c s dng rng ri trong nhiu lnh vc ha hc. N thng c s dng nghin cu mt lot cc qu trnh oxi ha kh, xc nh s n nh ca sn phm phn ng, s hin din ca cc cht trung gian trong phn ng oxi ha kh, phn ng v ng hc chuyn electron v s o ngc ca phn ng. CV cng c th c s dng xc nh h s t lng electron ca mt h thng, h s khuch tn ca mt cht phn tch v th kh ca mt cht phn tch, c th c s dng nh mt cng c nhn dng. Ngoi ra, bi v nng t l vi dng in trong h thng Nernstian nghch o, nng ca mt dung dch cha bit c th c xc nh bng cch to ra mt ng cong hiu chun nng so vi hin ti.Mt cuc nghin cu su rng v cc tnh cht oxi ha kh ca nhiu organofullerene khc nhau nh chc nng ha c bo co bi Suzuki v cng s, ngi nghin cu nh hng ca cc nhm chc gn trc tip C60 trn th CV. Mt hiu ng cm ng nh c tm thy, tnh c tit l nhng thay i trong th kh v oxy ha (nu c th) v ch yu lin quan n m in ca cc nguyn t gn vo.Cc h lin hp p ca C60 c v l tng cho ng dng quang hc phi tuyn tnh (nonlinear optical - NLO) (dng thay i bc sng trong cng nghip laser). Phn t c tnh cht NLO ln thng c c trng bi mt nhm cho electron v mt nhm rt electron hai u ca h lin hp p. V nguyn tc, s gn vo ca cc cht cho v cc cht nhn trong lin hp vi cc h thng p fullerene to nn hiu ng ko-y th v. Tuy nhin, hu ht cc phn ng ca fullerene dn n cc dn xut trong cht cng c gn vo C60 qua cacbon sp3 ph v h lin hp. Vn ny c kho lo x l bi Wudl v ng nghip, nhng ngi s dng h thng fluorenyl lin kt spiro vi nhm chc methanofullerene. Mt tng tc thng qua mt "c ch periconjugation gia cc nhm fluorene v hnh cu fullerene c pht hin bi voltammetry cyclic. Cc hnh vi in ho ca cc hp cht 7 l tng i nhy vi s hin din ca cc nhm th trn nhm chc fluorene. Vi cc nhm cho electron (7b) th kh c chuyn n cc gi tr m hn. Mt khc, th kh tr nn t m hn nu nhm ht electron mnh m c t trong nhm chc 9-fluorenyl (7c). Cc tnh cht in t ca spiromethanofullerene 7 c th c quy cho hnh hc c th ca n, nh b xng fluorenyl phng c t chc mt cch cng nhc vung gc vi b mt ca hnh cu. Sp xp c o ny c th chu trch nhim cho tng tc through-space gia cc nhm chc fluorenyl v khi cu, do tr nn nhy cm vi nhng thay i in t trong phn i fluorenyl. Cc phn t NLO ha hn 8 cng c tng hp di dng hn hp ca sn phm cng kp (R = cc nhm rt electron v cc nhm cho electron).

Hnh 38: phn t 7&8II.4.2. Tnh cht quang hcCc tnh cht hp th trng thi c bn ca C60, c trng bi cc di mnh trong vng UV v hp th yu trong vng kh kin n 650 nm, c gi li trong hu ht cc dn xut. Ngoi ra, dihydrofullerene m rng s hp th trong sut ton b vng nhn thy c vi hp th yu ti a khong 700 nm. Tnh nng b sung ny lm cho c th kch thch bng phng tin chiu x mc nng lng rt thp.Tng t vi C60, dihydrofullerene rt th v khi mt singlet tui th ngn chuyn i nhanh chng thnh mt trplet tn ti lu di, vi sn lng lng t hi thp hn so vi C60 . Trong khi C60 th hin mt b ba hp th triplet 750 nm, cc peak tng t chuyn sang 700 nm trong cc dn xut C60. S chuyn b ba-b ba ny c c trng bi mt h s hp th cao hn so vi trng thi c bn v c th phi chu trch nhim cho hnh vi phi tuyn tnh ca n. Theo , cc dung dch ca C60 v C70 th hin gii tnh cht quang hc gii hn (optical limit - OL), so snh rt tt vi nhng vt liu hin ti s dng. Tnh nng ny ha hn tuyt vi cho cc ng dng thc t, chng hn nh s hp nht ca cc dn xut fullerene trong hn hp trong sut thch hp cho bo v chng li cc xung laser nng lng cao. So vi C60, cc dn xut fullerene thy mt sn lng lng t singlet-triplet thp hn, v th d kin hiu sut OL thp hn. Tuy nhin, n c chng minh rng tnh cht hn ch quang hc ca C60 v cc dn xut ca n ph thuc vo s kch thch bc sng. Khi ci sau gn gi hn vi cc i hp thu b ba-b ba ca dn xut fullerene (700 nm) so vi s chuyn i tng ng C60 (750 nm), hiu sut OL ca organofullerene cng tr nn hiu qu. II.4.3. Sn phm cng aCc tnh cht ha l ca nhiu sn phm cng ph thuc rt ln vo s lng cht cng. Cc c tnh kh v oxy ha v ph thuc rt nhiu vo s lng v m hnh ca cc cht cng trong dn xut fullerene. Nh mt xu hng chung, cc dn xut fullerene tr nn kh khn hn kh i t sn phm cng mono n hexa. iu ny c quy cho cc lin hp gim xy ra trong cc hp cht fullerene a chc ha, dn n mt s gia tng tng ng vi nng lng ca cc LUMO. Xu hng tng t cng c quan st thy trong cc nghin cu tnh nng hp th ca UV-VIS, m s thay i do mt lin hp c quan st.II.5. Hot tnh sinh hc ca dn xut fullerene:Cc dn xut fullerene c nhiu c tnh sinh hc th v: Chng oxy ha Phn ct DNA Ph v mng Liu php quang ng Phn phi thuc (v d paclitaxel) Tc nhn tng phn X-ray S c ch b-amyloid kt t Bt bin gc t do: bo v nron Khng khun Thm chuyn gene Enzyme c ch (HIVP, vv)Liu php quang ng (PDT), i khi c gi l photochemotherapy, l mt hnh thc tr liu quang hc s dng hp cht nhy sng khng c hi c tip xc vi nh sng c chn lc v ri n tr thnh c hi nhm mc tiu cc t bo c tnh v cc t bo bnh khc (phototoxicity). PDT chng minh kh nng tiu dit cc t bo vi sinh vt, bao gm vi khun, nm v virus. PDT c s dng ph bin trong iu tr mn trng c. N c s dng trn lm sng iu tr mt lot cc iu kin y t, bao gm c thoi ha im vng tui gi v bnh ung th c tnh v c cng nhn nh l mt chin lc iu tr c c xm ln ti thiu v c hi ti thiu.Amyloid beta (A hay Abeta) biu th cc peptide ca cc axit amin 36-43 lin quan ch yu n bnh Alzheimer l thnh phn chnh ca cc mng amyloid tm thy trong no ca bnh nhn Alzheimer. Cc peptide kt qu t cc tin cht protein amyloid (APP), hin ang c ct bi cc enzyme nht nh sn xut A. Phn t A c th kt hp to thnh oligome linh hot tan m c th tn ti trong nhiu hnh thc. Cc nh khoa hc tin rng nht nh oligomer b gp li (misfolded) (c gi l "ht ging") c th gy ra cc phn t linh hot khc cng mang hnh thc oligomer misfolded, dn n mt phn ng dy chuyn ging nh mt prion (mt protein c th gp nhiu ln, c th ly sang protein prion khc. N l hnh thc nhn rng dn n nhng cn bnh tng t nh nhim virus). Cc ht ging hay cc mng amyloid to thnh c hi i vi cc t bo thn kinh. Cc protein khc lin quan n bnh Alzheimer, protein tau, cng to oligomer misfolded prion nh th v c mt s bng chng cho thy misfolded A c th gy ra tau misfold.Thm chuyn (transfection) l qu trnh c tnh a cc axit nucleic vo cc t bo. Transfection ca t bo ng vt c trng lin quan n m 1 l tm thi trn mng t bo cho php s hp thu ca vt liu. Thm chuyn c th c thc hin bng cch s dng calcium phosphate, bi electroporation (hoc electropermeabilization l mt k thut sinh hc phn t, trong mt in trng c p dng cho cc t bo lm tng tnh thm ca mng t bo, cho php ha cht, thuc, hoc DNA c a vo t bo), bi p t bo hoc bng cch trn mt lipid cation vi cc vt liu sn xut cc liposome, m kt hp c vi cc mng t bo v gi hng ha ca n vo bn trong. Thm chuyn c th dn n hnh thi bt ng v bt thng trong t bo mc tiu. ng vt v thc vt bin i gene c th c to ra theo cch ny.Mt protease (cn gi l peptidase hay proteinase) l bt k enzyme m thc hin phn gii protein, bt u qu trnh d ha protein bng cch thy phn lin kt peptide lin kt axit amin vi nhau trong mt chui polypeptide. Protease tin ha nhiu ln v cc lp khc nhau ca cc protease c th thc hin phn ng tng t bi c ch xc tc hon ton khc nhau. Protease c th c tm thy trong ng vt, thc vt, vi khun, vi khun c v vi rt.HIV-1 protease l mt aspartyl protease (retropepsin) cn thit cho vng i ca HIV, cc retrovirus gy bnh AIDS. HIV protease tch ra polyprotein tng hp mi v tr thch hp to ra cc thnh phn ca protein trng thnh ca mt virus HIV ly nhim. Nu khng c protease HIV hiu qu, virus HIV vn khng ly nhim. Nh vy, t bin ca tm hot ng protease HIV hoc c ch hot ng ca n s ph v kh nng ti to HIV v ly nhim sang t bo khc.III. ng dng tim nng ca fullereneKhi mn b mt C60 c vn m, ngi ta ngh ngay n nhng p dng thc tin ca C60. Ngi ta kt hp C60 vi kali to ra cht siu dn hu c nhit 18K (-256C). Mt s nh nghin cu sinh hc hy vng c th dng C60 iu ch dc phm tr liu bnh AIDS. Trong vt l, rt nhiu ngh p dng C60 ch to nhng dng c quang in t trong cng ngh cao. Tuy nhin, trn mt p dng cc nh khoa hc thng mc phi mt cn bnh chung l "lc quan qu ". Cu trc trn tra, i xng ca C60 c tp chSciencetn vinh l "phn t ca nm 1991", nhng ci xinh p hp dn khng phi lc no cng a n kt qu thc tin hon m.Hai yu t lm C60 gim tnh thc t l: (1) gi c qu cao (gi cho 1 gram l vi trm USD hoc cao hn cho tinh cht (sublimed), so vigi vng vo khong $10/g v (2) C60 khng ha tan trong dung mi rt bt li cho vic x l. Nhng h hi ban u trong cng ng nghin cu khoa hc dnh cho fullerene b dp tc nhanh chng v nhng tr ngi ny.Thm ch ngay trong cng ngh "thp", chng hn dng C60 nh mt cht ph gia cho du nht lm gim ma st vn khng ch ni v gi c v hiu qu ca nhng cht ph gia thng thng. Tun boThe economistc ln ph bnh"Ci cng ngh duy nht m qu bng bucky thc s cch mng lsnxut nhng bi bo co khoa hc"(The only industry the buckyball has really revolutionized is the generation ofscientific papers)!Nhng vin nh ca C60 trong p dng cng ngh khng n ni tm ti nh cc nh bnh lun kinh t hp tp d on. S kin tr ca nhng ngi lm khoa hc lc no cng cho thy mt nim lc quan ca "nhng tia sng cui ng hm".Cng ty Nano-C (M) c kh nng sn xut hng tn C60 cho giicng ngh. Mt nh my ti Nht ang c kh nng ch to 40 tn hng nm v s ln n vi trm tn khi nh my c nng cp. Phng php sn xut hng lot s lm gim gi C60 t 23$/g (C60 99%) nh hin nay n mc $5/g v c th $1/g trong mt tng lai khng xa. y l mt bc nhy v i so vi nhng nm u thp nin 90 khi ngi ta ch thu lm vi miligram C60 mi ln tng hp kh khn v gi cho mi gram c lc ln n $1500/g. Nh sn xut d on nhu cu C60 s tng nhanh trong vi nm ti cho vic ch bin dc liu, du nht cao cp v m phm trang im gp phn tng qui m sn xut v gim gi thnh, do kh khn (1) c th vt qua.

Hnh 39: gi bn C60 v C70 hin nay (BuckyUSA)i vi kh khn (2), cc kh nng x l ca fullerene th hin mt vn ln trong cn st tm kim cc ng dng thc t. C60 khng ha tan hoc ch t ha tan trong dung mi v kt t rt d dng. Tr ngi nghim trng ny c th c, t nht l mt phn, vt qua vi s gip ca s chc nng ha fullerene. Cc dn xut hu c ca C60 a ra mt s lng ngy cng nhiu, trong khi vn gi li hu ht cc c tnh ban u ca fullerene, tr nn d dng hn nhiu x l.III.1. Quang in hu c (Organic Photovoltaic OPV) - Pin mt tri[2, 5]Kh nng p dng fullerene trong cng ngh cao lin quan n quang hc v quang in t ang c tch cc kho st nhiu c quan nghin cu trn th gii. Mttrong ng dng c tm quan trng c bit lc tnh quang in ca C60 tc l kh nng sn xut pin mt tri.Loi pin ny c ch to t C60 v polymer dn in (electrically conducting polymers). Hnh 40: PCBM

i lc electron cao v kh nng cao cp v vn chuyn in tch khin cho fullerene l cu t nhn (acceptor) tt nht hin nay. u tin, n c mt LUMO nm su mnh m lm cho cc phn t c i lc electron rt cao lin quan n rt nhiu cc cht hu c cho (donor) tim nng. LUMO ca C60 cng cho php cc phn t kh thun nghch ln n su electron, do c kh nng ca in tch m bn vng. Quan trng hn, mt s lin hp hn hp polymer-fullerene c bit th hin chuyn in tch cm ng quang cc nhanh vi s chuyn tr li c cng bc thp hn. Hin nay ph bin trong lnh vc quang in hu c l cc t bo nng lng mt tri Bulk Heterojunction (BHJ) da trn fullerene dn xut phenyl Cn butyric axit methyl ester (PCBM).Hnh 41:s pin nng lng mt tri hu c 1 lp

Hnh trn l mt s ca pin nng lng mt tri hu c 1 lp. Fullerene ng vai tr l loi cht bn dn n (nhn in t). Cc loi n c s dng kt hp vi mt loi p polymer (cho in t) nh polythiophene. Chng c pha trn v ng vai lp hot ng to ra nhng g c bit n nh khi ni k d. Fullerene c s dng ring hoc dn xut tng tan ca n v bin tnh cc thuc tnh in t ca n. Dn xut thng c s dng trong quang in l C60, nhng C70 c chng minh c hiu sut chuyn i nng lng cao hn 25% so vi C60. Ngoi ra, thay th cc dn xut nh C60 PCBB c th hin tng hiu sut chuyn i hn 40% khi so snh vi C60 PCBM trong cc h thng nh vy. Vo thng mi mt nm 2005 hiu sut pin k lc 4,4% s dng mt dn xut fullerene v minh ha tm quan trng ca cc c im ca cc lp hot ng trn hiu nng c cng b. L vt liu loi n a thch, thnh phn fullerene c th ln n 75% ca cc lp hot ng theo trng lng. Cc tim nng tng hiu qu thit b thng qua phn ho cht fullerene mi tip tc m rng. Cc hot ng ca transistor polymer v d Organic Field Effect Transitor (OFETS) v cm bin quang cng c tng ln, mt phn l do mt lng ln nng lng gia OFETS v OPVs. Cc OFETS dn s dng bn dn loi n ca fullerene da trn C60, C70 cng vi C84. Fullerene OFETS ch to vi C84 cho thy tnh di ng ln hn C60 hoc C70 v th hin tnh n nh cao hn. Hiu sut thit b tip tc tng v cc lnh vc tip tc thu ht u t t cc cng ty ln v nh nh nhau. T hiu qu pin l 5% trong nm 2005, h t tng ln 12% vo nm 2013. Cc lnh vc OPV hin nay bao gm Eight19, Heliatek, New Energy Technology, Plextronics, Inc., Solarmer Energy, Inc., v Solar-Press. V thm vo , cc cng ty ln ang u t vo lnh vc ny ca chnh h cng nh trong cc d n chung; trong s l BASF, Bosch, Merck, Mitsubishi Chemical v Phillips66. Vi mc cao ca nghin cu thng mi v hc thut, chng ta s tip tc chng kin mc tng trong hiu qu v tui th. Kt hp vi s ch to roll-to-roll, li nng lng mt tri hu c cnh tranh l trong tm tay. Cc t bo nng lng mt tri silicon thng thng vt qu hiu sut 20% nhng cc chi ph sn xut thit b chuyn i nh sng hu c so vi thit b v c tng t thp hn hai bc theo s m. V c tnh quan trng ca cc t bo nng lng mt tri hu c l tnh linh hot. N c th cun li, ct v tri rng trn mi b mt. Nhng loi pin mang bt k mu sc v kt cu c th c sn xut c bit c s dng bao gm c cc bc tng bn trong v bn ngoi ca ta nh. Mt in thoi di ng c th c sn vi cht liu ny, do i b trong mt ngy nng s l sc pin ca thit b. Cc phng ban qun s ca M tch cc cc d n h tr kt hp vi cc t bo nng lng mt tri hu c do cc ti liu chng minh kh nng cao s c s dng trong mi v kh v cc h thng h tr.Detector quang hu c (Organic Photodetector OPD) l cc thit b cm nhn nh sng c th c s dng trong cc ng dng t iu khin chuyn ng cho hnh nh y t. Ging nh OPV, chng c th mng, trng lng nh, linh hot, c th in c v chi ph thp. Detector thng thng thng c lm t silicon da trn cht bn dn v do s dng cc qu trnh lng ng chn khng nhit cao. Ngc li, qu trnh sn xut ca ODP da trn nhit thp, p sut kh quyn v in n h dung dch trn thy tinh hoc nha. Nh pht trin ca OPD gm ISORG, NikkoIA SAS v Siemens cng vi cc vin nghin cu nh IMEC. Ngoi ra, cc cng ty nh GE v Universal Display ang lm vic tch hp cc loi my d vo thit b ca h.Cui cng, nhng k vng ln cng lin quan vi vic s dng ca cc pin hu c trong cc qung co v kinh doanh bao b, lin quan n biu ng t pht sng, hin th dng tinh th lng ln v bao b cho thc phm.III.2. Lu tr hydro[5]Do cu trc phn t c o ca n, fullerene ch to thnh t carbon, c tim nng c th c hydro ha v dehydro ha thun nghch. Khi fullerene c hydro ha, cc lin kt i C = C tr thnh lin kt n C-C v C-H. mnh ca lin kt n C-C l 83 kcal/mol, v cc tnh ton l thuyt cho thy rng mnh ca lin kt C-H hydro ha l 68 kcal/mol. iu ny c ngha rng trong hirua fullerene, lin kt H-C yu hn lin kt C-C. V vy, khi nhit c p dng cho cc hirua fullerene, lin kt H-C s ph v trc cc lin kt C-C v cc cu trc fullerene c m bo. Nhit hnh thnh thp hn ng k ca C60H36 ch ra rng C60H36 l mt phn t l bn nhit tt hn hn so vi C60. V vy, hydro ca C60 l thun li v nhit ng v c th c hon thnh ngay di cc iu kin ha hc thng thng. Cc mu sc ca cc fullerene hydro ha thay i t mu en sang mu nu, sau n mu , cam, v nh sng mu vng vi tng lng hydro. Fullerene ln n 6,1% hm lng hydro c pht trin thc nghim. Mt ng dng tim nng ca fullerene hirua l trong thit b lu tr kh hydro cho xe in s dng mt pin nhin liu. Hin nay c sn cng ngh lu tr hydrogen nh kh nn hoc lu tr nh hirua kim loi nhng nguy him tim tng v/hoc c mt lu tr hydrogen thp. Bng cho thy mt so snh s lng phng tin cn thit cho lu tr khi s dng Fullerene so vi mt hydride kim loi. Phng tin lu tr hydride kim loi c s dng trong so snh ny l Titanium Zirconium Vanadium.

Bng 2: So snh kh nng cha hydro cho ng c t trong

FullerenHydride kim loi

Hydro yu cu cho vn hnh 250 dm12lb12lb

Lng phng tin lu tr cn thit197lb1200lb

Mt phng php lu tr hydro khc qua con ng tng hp exohedral fullerene: cc phn t kim loi hu c fullerene doping boron C48B12. Kim loi chuyn tip lin kt vi fullerene c xut nh l cc cht hp ph cho lu tr hydro mt cao, nhit phng v p sut kh quyn. C60 hoc C48B12 phn tn kim loi chuyn tip bng tng tc chuyn in tch sn xut buckyball kim loi hu c n nh (OBBs). Mt OBB scandium c bit c th gi n 11 nguyn t hydro mi kim loi chuyn tip, mi trong s l dng dihydrogen c th c hp th v gii hp thun nghch. Trong trng hp ny, nng lng lin kt tnh l khong 0.3 eV/H2, l l tng s dng trn cc phng tin giao thng ln (tu, tu ha v my bay). Mt lu tr H2 c th phc hi c ti a l thuyt l 9% trng lng. Cc phc C60[ScH2(H2)4]12 v C48B12[ScH(H2)5]12 n nh, c th hp th thun nghch thm hydrogen. Doping vi boron gip gim khi lng fullerene, tng cng s n nh phc bng cch tng nng lng lin kt v cho php cc rng buc thm mt phn t H2 mi Sc, tng lng H2 c th phc hi c[6].

Hnh 42: lu tr hydro bng exohedral fullereneIII.3. ng dng quang hcHn ch quang (optical limit) cp n vic gim h s truyn qua ca mt vt liu lm tng cng nh sng ti. Cc hin tng quang hc hn ch c tim nng ng k ng dng trong bo v mt v cm bin t cc ngun d di ca nh sng. Da vo tnh cht hn ch quang fullerene c th lm ra mt vt gii hn quang cho php tt c cc nh sng bn di mt ngng kch hot vt qua v duy tr cc nh sng truyn mt mc lin tc di ngng gy hi cho mt hay cm bin. Hnh 43 cho thy vic thc hin tiu biu ca mt gii hn quang:

Hnh 43:Tnh cht chuyn gii hn quang hcNhng tin b trong cng ngh bn dn c lin quan trc tip n kh nng pht trin tnh cn quang (photo-resist) to ra sn phm c th c s dng m hnh mch trn tm silicon vi kch thc gim xung di 20nm. Cn quang thng c lm bng polyme nhng gii hn ca h thng polymer t c gii hn do trng lng phn t ca polymer. Th h tip theo ca sn quang c gi l cn phn t (molecular-resists) m fullerene c u th ln kim sot kch thc tnh nng v phn gii. u im l do kch thc ca chng