Glycerol valorisation as biofuel: Glycerol acetals production by Simulated Moving Bed Reactor
Full text
)DFXOGDGHGH(QJHQKDULDGD8QLYHUVLGDGHGR3RUWR *O\FHUROYDORULVDWLRQDVELRIXHOV *O\FHURODFHWDOVSURGXFWLRQE\6LPXODWHG0RYLQJ %HG5HDFWRU 'LVVHUWDWLRQ3UHVHQWHGWR)DFXOGDGHGH(QJHQKDULDGD8QLYHUVLGDGHGR3RUWRIRUWKH GHJUHHRI3K'LQ&KHPLFDODQG%LRORJLFDO(QJLQHHULQJ E\ 5XL3HGUR9LHLUD)DULD 6XSHUYLVRU3URI'U$OtULR(5RGULJXHV &RVXSHUYLVRU'U&DUOD603HUHLUD /DERUDWRU\RI6HSDUDWLRQDQG5HDFWLRQ(QJLQHHULQJ$VVRFLDWH/DERUDWRU\/65(/&0 'HSDUWPHQWRI&KHPLFDO(QJLQHHULQJ)DFXOW\RI(QJLQHHULQJ8QLYHUVLW\RI3RUWR
)(83/65(/&08QLYHUVLGDGHGR3RUWR 5XL3HGUR9LHLUD)DULD $OOULJKWVUHVHUYHG
$FNQRZOHGJPHQWV )LUVW DQGIRUHPRVW,ZLVK WRWKDQNWR P\VXSHUYLVRU3URIHVVRU$OtULR5RGULJXHVIRUKLV YDOXDEOH DGYLFHV DQG LQVLJKWV ,W LV UHDOO\ D SOHDVXUH WR ZRUN ZLWK VRPHRQH ZLWK VR PXFK NQRZOHGJHWRVKDUH ,DOVRRZHP\GHHSHVWJUDWLWXGHWR'U&DUOD3HUHLUDP\FRVXSHUYLVRUZKRGHYRWHGVR PXFKRIKHUSUHFLRXVWLPHDQGDWWHQWLRQZKHQHYHU,UHTXHVWHG,WZDVIRUVXUHWKDWNLQGRI GHGLFDWLRQ DQG FRPPLWPHQW WKDW PDGH KHU VXFK D UHPDUNDEOH SURIHVVLRQDO« DQG DQ H[WUDRUGLQDU\SHUVRQ 7KHUHVHDUFKOHDGLQJWRWKHUHVXOWVSUHVHQWHGLQWKLV7KHVLVZRXOGQRWEHSRVVLEOHZLWKRXW WKH ILQDQFLDO VXSSRUW IURP WKH (XURSHDQ 8QLRQ 6HYHQWK )UDPHZRUN 3URJUDPPH )3 XQGHU*UDQW$JUHHPHQW(XUR%LR5HI 7KH UHOHYDQW FRQWULEXWLRQV RI 'U 9LYLDQD 6LOYD DQG 3URIHVVRU -RVp 0LJXHO /RXUHLUR HVSHFLDOO\DWWKHHDUOLHUVWDJHVRIP\3K'FDQQRWEHIRUJRWWHQDVZHOO ,ZRXOGDOVROLNHWRWKDQNDOOP\3URIHVVRUVDQGFROOHDJXHVDWWKH/65(IRUWKHLUNLQGQHVV DQG VXSSRUW , IHHO YHU\ IRUWXQDWH IRU EHLQJ D SDUW RI VXFK D TXDOLILHG DQG SURIHVVLRQDO UHVHDUFKWHDP ,WLVZLWKLPPHQVHJUDWLWXGHWKDW,DFNQRZOHGJHWKHKHOSRIP\IHOORZODEPDWHV'k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
5HVXPR 2SULQFLSDOREMHWLYRGDLQYHVWLJDomRGHVHQYROYLGDDRORQJRGRSUHVHQWHSURJUDPDGRXWRUDO IRL D YDORUL]DomR GR JOLFHURO REWLGR FRPR H[FHGHQWH GXUDQWH R SURFHVVR GH SURGXomR GH ELRGLHVHO DWUDYpV GD VXD WUDQVIRUPDomR HP DFHWDO HWtOLFR GH JOLFHURO *($ UHFRUUHQGR DR UHDWRU GH OHLWR PyYHO VLPXODGR FRPR HVWUDWpJLD GH LQWHQVLILFDomR GH SURFHVVRV WHQGR HP YLVWDDLPSOHPHQWDomRGHXPSURFHVVRLQGXVWULDOHILFLHQWHHVXVWHQWiYHO3DUDHVWHHIHLWRIRL QHFHVViULD D VHOHomR GH XP FDWDOLVDGRUDGVRUYHQWH DGHTXDGR H D REWHQomR GH GDGRV IXQGDPHQWDLV GD FLQpWLFD GD UHDomR TXtPLFD GH VtQWHVH GR UHIHULGR DFHWDO H GH GDGRV GH DGVRUomRGHWRGRVRVFRPSRVWRVGHVWHVLVWHPDUHDFLRQDOXVDQGRRVyOLGRHVFROKLGR 1XPD SULPHLUD IDVH IRL HODERUDGR XP HVWXGR HQYROYHQGR WHVWHV FLQpWLFRV D FDWDOLVDGRUHVGLVSRQtYHLVFRPHUFLDOPHQWH]HyOLWRVHUHVLQDVGHSHUPXWDLyQLFDWHQGRVLGR VHOHFLRQDGDDUHVLQDGHSHUPXWDLyQLFD$PEHUO\VWZHW3URFHGHXVHDRHVWXGRGHWDOKDGR GD UHDomR HQWUH JOLFHURO H DFHWDOGHtGR QXP UHDWRU IHFKDGR GHWHUPLQDQGR RV SULQFLSDLV SDUkPHWURV GH HTXLOtEULR WHUPRGLQkPLFR H FLQpWLFRV WHQGR VLGR SURSRVWR R PRGHOR GH /DQJPXLU+LQVKHOZRRG+RXJHQ:DWVRQ SDUD D OHL GH YHORFLGDGHV 6HJXLGDPHQWH IRL GHVHQYROYLGD XPD PHWRGRORJLD SDUD D HVFROKD GH VROYHQWHV SDUD SURFHVVRV LQWHJUDGRV GH UHDomRDGVRUomR$DSOLFDomRGHVWDPHWRGRORJLDDRVLVWHPDHPHVWXGRSHUPLWLXLGHQWLILFDUR GLPHWLO VXOIy[LGR FRPR R VROYHQWH PDLV DSURSULDGR WHQGRVH DQDOLVDGR R LPSDFWR GD LQWURGXomRGHVWDHVSpFLHQRPHLRUHDFLRQDO 'DGRV UHODWLYRV DR HTXLOtEULR GH DGVRUomR IRUDP REWLGRV DWUDYpV GH WHVWHV QXPD FROXQD FURPDWRJUiILFD UHFRUUHQGR D XPD PHWRGRORJLD GH DQiOLVH IURQWDO H RV UHVXOWDGRV IRUDP DMXVWDGRVDXPDLVRWpUPLFDGH/DQJPXLUPXOWLFRPSRQHQWH $HVWUDWpJLDGHLQWHQVLILFDomRGHSURFHVVRVDGRWDGDEDVHDGDQDLQWHJUDomRGHSURFHVVRV GHDGVRUomRHUHDomRSHUPLWLXHIHWXDUDVtQWHVHGH*($QXPUHDWRUFURPDWRJUiILFRFRQWtQXR GHOHLWRIL[R $WUDYpV GD UHDOL]DomR GH HQVDLRV H[SHULPHQWDLV QXP UHDWRU GH OHLWR PyYHO VLPXODGR j HVFDODSLORWRGHPRQVWURXVHTXHDSURGXomRGH*($DWUDYpVGHVWDWHFQRORJLDpSRVVtYHO 0RGHORV PDWHPiWLFRV FRPSOH[RV FRQWHPSODQGR IHQyPHQRV GH WUDQVIHUrQFLD GH PDVVD UHDomR H DGVRUomR IRUDP GHVHQYROYLGRV SDUD FDGD XPD GDV WHFQRORJLDV DQWHULRUPHQWH UHIHULGDV UHDWRU IHFKDGR UHDWRU FURPDWRJUiILFR GH OHLWR IL[R H UHDWRU GH OHLWR PyYHO
VLPXODGRSHUPLWLQGRQmRVyDSURIXQGDURFRQKHFLPHQWRDFHUFDGHFDGDXPGHVWHVSURFHVVRV PDVWDPEpPSURFHGHUjRWLPL]DomRGDVVXDVFRQGLo}HVGHRSHUDomR
Y /LVWRI)LJXUHV )LJXUH²:RUOGUHJLVWHUHGDQGSUHGLFWHGHQHUJ\FRQVXPSWLRQEHWZHHQDQG )LJXUH&RQYHQWLRQDOJO\FHURODSSOLFDWLRQVDGDSWHG )LJXUH²*O\FHUROJOREDOSURGXFWLRQDQGSULFHVHYROXWLRQDGDSWHG )LJXUH²*($PHPEHUHGULQJLVRPHUDDQGFDQGPHPEHUHGULQJLVRPHUE DQGG )LJXUH²6FKHPHIRUWKHUHDFWLRQPHFKDQLVPRIWKHFRQGHQVDWLRQRIJO\FHUROZLWK DFHWDOGHK\GH )LJXUH²)ORZVKHHWIRUWKHFRQWLQXRXVSURGXFWLRQRIELRGLHVHOFRQWDLQLQJDJO\FHURO DFHWDODGGLWLYHREWDLQHGE\DQDFHWDOL]DWLRQUHDFWLRQDGDSWHG )LJXUH²)ORZVKHHWIRUWKHFRQWLQXRXVSURGXFWLRQRIELRGLHVHOFRQWDLQLQJDJO\FHURO DFHWDODGGLWLYHREWDLQHGE\WUDQVDFHWDOL]DWLRQUHDFWLRQDGDSWHG )LJXUH²*($LVRPHUVLQWHUFRQYHUVLRQLQWKHSUHVHQFHù − ⋅ PRO GP RI SHUFKORULFDFLGLQEHQ]HQHDW . DGDSWHG )LJXUH²,VRPHUVUDWLRHYROXWLRQGXULQJWKHV\QWKHVLVRI*($DW . DGDSWHG )LJXUH²7HPSHUDWXUHSURILOHDORQJWLPHIRUFXUUHQWO\XVHG)6,,DQGF\FOLFDFHWDOV IURPJO\FHURODGDSWHG )LJXUH²6FKHPHRID70%5DDQGD60%5EXQLW )LJXUH6HWXSXVHGIRUWKHUPRG\QDPLFHTXLOLEULXPH[SHULPHQWV )LJXUH6FKHPHRIWKHVHWXSXVHGIRUNLQHWLFH[SHULPHQWV )LJXUH/LQHDUL]DWLRQRIWKHYDOXHVRIHTXLOLEULXPFRQVWDQWVDFFRUGLQJWR9DQ·W+RII HTXDWLRQ )LJXUH(YROXWLRQRIWKHHTXLOLEULXPFRQVWDQWRIWKHDFHWDOL]DWLRQRIJO\FHUROZLWKWKH OHQJWKRIWKHDOGHK\GHFKDLQ )LJXUH&DWDO\VWSHUIRUPDQFHVLQWHUPVRIJO\FHUROFRQYHUVLRQDIWHU K DQG K 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RI FDWDO\VW
YL )LJXUH&DWDO\VWVSHUIRUPDQFHVLQWHUPVRIJO\FHUROFRQYHUVLRQRYHUDQ K SHULRG 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RI FDWDO\VW )LJXUH²(IIHFWRIWKHVWLUULQJVSHHGLQWKHUHDFWLRQUDWHDVDPHDVXUHPHQWRIH[WHUQDO PDVVWUDQVIHUOLPLWDWLRQV 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHURO PRODUUDWLR ZW RIXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWKHFDWDO\VWDPRXQWRQWKHUHDFWLRQUDWH 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLRXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWHPSHUDWXUHRQWKHUHDFWLRQUDWH 3 EDU = LQLWLDO DFHWDOGHK\GHJO\FHUROPRODUUDWLRXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWKHLQLWLDOUHDFWDQWPRODUUDWLRRQWKHUHDFWLRQUDWH 7 . = 3 EDU = ZW RIXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRQWKHUHDFWLRQUDWHRIWKHSUHVHQFHRISURGXFWVLQWKHLQLWLDOPL[WXUH 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RIXQVLHYHG $PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIFDWDO\VWSDUWLFOHVL]HRQWKHUHDFWLRQUDWH 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RI$PEHUO\VWVWLUULQJ VSHHGRI USP )LJXUH(IIHFWRISDUWLFOHVL]HRQFRQYHUVLRQSURILOHLQVLGHWKHFDWDO\VW PLQ DIWHU WKHEHJLQQLQJRIWKHUHDFWLRQ 7 . = 3 EDU = LQLWLDO DFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RIXQVLHYHG$PEHUO\VW )LJXUH7HUQDU\SKDVHGLDJUDPIRUJO\FHURODFHWRQLWULOHZDWHUDQG JO\FHURODFHWRQLWULOH*($PL[WXUHVLQPRODUFRPSRVLWLRQVDW . )LJXUH$GVRUSWLRQRQ$PEHUO\VWGHWHUPLQHGE\VZHOOLQJWHVWVSHUIRUPHGDW . IRU K )LJXUH&RPSDULVRQRIWKHSHUIRUPDQFHRIWKHVROYHQWVRQWKHNLQHWLFVRIWKH DFHWDOL]DWLRQUHDFWLRQ 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHURO PRODUUDWLRVROYHQWPRODUIUDFWLRQRI ZW RIWKHWRWDOUHDFWDQWVPDVVRI XQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWKHVWLUULQJVSHHGLQWKHUHDFWLRQUDWHDVDPHDVXUHPHQWRIH[WHUQDO PDVVWUDQVIHUOLPLWDWLRQV 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHURO PRODUUDWLRVROYHQWPRODUIUDFWLRQRI ZW RIXQVLHYHG$PEHUO\VW VWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWHPSHUDWXUHRQWKHUHDFWLRQUDWH 3 EDU = LQLWLDO DFHWDOGHK\GHJO\FHUROPRODUUDWLRVROYHQWPRODUIUDFWLRQRIVWLUULQJVSHHGRI USP )LJXUH(IIHFWRIWKHUHDFWDQWVPRODUUDWLRRQWKHUHDFWLRQUDWH 7 . = 3 EDU = VROYHQWPRODUIUDFWLRQRIVWLUULQJVSHHGRI USP
YLL )LJXUH(IIHFWRIWKHVROYHQWPRODUIUDFWLRQRQWKHUHDFWLRQUDWH 7 . = 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLRVWLUULQJVSHHGRI USP )LJXUH²6FKHPHRIWKHVHWXSXVHGIRUWUDFHUDQGEUHDNWKURXJKH[SHULPHQWV )LJXUH²6FKHPHRIWKHIL[HGEHGFROXPQDDQGWKHPDVVWUDQVIHUPHFKDQLVP EHWZHHQWKHEXONIOXLGDQGWKHFDWDO\VWDGVRUEHQWSDUWLFOHVE )LJXUH7UDFHUUHVLGHQFHWLPHGLVWULEXWLRQFXUYHV )LJXUH/DQJPXLUFRPSHWLWLYHDGVRUSWLRQLVRWKHUPIRUWKHELQDU\JO\FHUROD²'062 ERYHU$PEHUO\VWDW . )LJXUH/DQJPXLUFRPSHWLWLYHDGVRUSWLRQLVRWKHUPIRUWKHELQDU\:DWHUD²'062 ERYHU$PEHUO\VWDW . )LJXUH/DQJPXLUFRPSHWLWLYHDGVRUSWLRQLVRWKHUPIRUWKHELQDU\*($D²'062E RYHU$PEHUO\VWDW . )LJXUH([SHULPHQWDODQGSUHGLFWHGEUHDNWKURXJKFXUYHVIRUWKHELQDU\JO\FHURO '062DW . DQGDIORZUDWHRIDSSUR[LPDWHO\ P/ PLQ − ⋅ )LJXUH([SHULPHQWDODQGSUHGLFWHGEUHDNWKURXJKFXUYHVIRUWKHELQDU\ZDWHU'062 DW . DQGIORZUDWHVRIDSSUR[LPDWHO\ P/ PLQ − ⋅ DDQG P/ PLQ − ⋅ E )LJXUH([SHULPHQWDODQGSUHGLFWHGEUHDNWKURXJKFXUYHVIRUWKHELQDU\*($'062DW . DQGIORZUDWHVRIDSSUR[LPDWHO\ P/ PLQ − ⋅ DDQG P/ PLQ − ⋅ E )LJXUH²6\QWKHVLVRI*($LQDIL[HGEHGDGVRUSWLYHUHDFWRUDW . E\IHHGLQJD VROXWLRQFRQWDLQLQJ − ⋅ PRO / RIDFHWDOGHK\GH − ⋅ PRO / RIJO\FHURODQG − ⋅ PRO / RI'062DW − ⋅ P/ PLQ DDQGUHJHQHUDWLRQRIWKHEHGZLWKSXUH '062DW − ⋅ P/ PLQ E )LJXUH²,QWHUQDOFRQFHQWUDWLRQSURILOHVRIWKHIL[HGEHGDGVRUSWLYHUHDFWRU PLQ D P LQ E PLQ FDQG PLQ GDIWHUWKHEHJLQQLQJRIWKHV\QWKHVLVRI*($E\ IHHGLQJDVROXWLRQFRQWDLQLQJ − ⋅ PRO / RIDFHWDOGHK\GH − ⋅ PRO / RI JO\FHURODQG − ⋅ PRO / RI'062DW − ⋅ P/ PLQ = 7 . )LJXUH(IIHFWRIVSDFHWLPHRQWKHPD[LPXPDFKLHYDEOHFRQYHUVLRQIRUWKH V\QWKHVLVRI*($LQDIL[HGEHGDGVRUSWLYHUHDFWRU = 7 . =3H DFHWDOGHK\GHJO\FHURO'062PRODUUDWLRRI )LJXUH([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DWD IORZUDWHRI − ⋅ P/ PLQ WRDIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DW . )LJXUH([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WR DIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DW .
YLLL )LJXUH([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DWD IORZUDWHRI − ⋅ P/ PLQ WRDIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DW . )LJXUH([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WR DIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DW . )LJXUH²6FKHPDWLFFRPSDULVRQEHWZHHQ70%5DDQG60%5ERSHUDWLRQPRGH )LJXUH²/,&26(360%5SLORWXQLW )LJXUH²([WUDFWDDQGUDIILQDWHEH[SHULPHQWDOFRQFHQWUDWLRQKLVWRU\ )LJXUH²([SHULPHQWDO60%5LQWHUQDOFRQFHQWUDWLRQSURILOHVDWWKHILUVWWKLUGDQG WZHOIWKF\FOHVF\FOLFVWHDG\VWDWHKLJKOLJKWHGZLWKDGRWWHGOLQH )LJXUH²([SHULPHQWDODQGVLPXODWHG60%5LQWHUQDOFRQFHQWUDWLRQSURILOHVDWWKH F\FOLFVWHDG\VWDWH = 7 . = ) $F [ = ) *O\ [ = ) '062 [ = ' '062 [ − = ⋅ ) 4 P/ PLQ − = ⋅ ' 4 P/ PLQ − = ⋅ ; 4 P/ PLQ − = ⋅ 5 4 P/ PLQ − = ⋅ 5HF 4 P/ PLQ = V W PLQ DQGDFRQILJXUDWLRQ )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLFVWHDG\ VWDWHFRQVLGHULQJDGHYLDWLRQRI ± RQWKHUDIILQDWHVWUHDPIORZUDWH 5 4 P/ PLQ − = ⋅ DDQG 5 4 P/ PLQ − = ⋅ E )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLFVWHDG\ VWDWHFRQVLGHULQJDGHYLDWLRQRI ± RQWKHUHF\FOLQJVWUHDPIORZUDWH )LJXUH²,QILQLWHGLOXWLRQGLIIXVLRQFRHIILFLHQWIRUJO\FHURODFHWDOGHK\GHZDWHUDQG *($LQ'062DW . HVWLPDWHGE\GLIIHUHQWFRUUHODWLRQV )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLFVWHDG\ VWDWHFRQVLGHULQJWKH6LGGLTL/XFDVFRUUHODWLRQIRUWKHHVWLPDWLRQRIWKHGLIIXVLYLWLHV )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLF VWHDG\VWDWHFRQVLGHULQJWKH0DFNLH0HDUHVHTXDWLRQIRUWKHHVWLPDWLRQRIWKH WRUWXRVLW\ )LJXUH²*O\FHURODFHWDOGHK\GHZDWHU*($DQG'062H[WHUQDOPDVVWUDQVIHU FRHIILFLHQWVHVWLPDWHGE\GLIIHUHQWFRUUHODWLRQV )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLF VWHDG\VWDWHFRQVLGHULQJWKH'ZLYHGL8SDGK\D\FRUUHODWLRQIRUWKHHVWLPDWLRQRIWKH H[WHUQDOPDVVWUDQVIHUFRHIILFLHQWV )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLF VWHDG\VWDWHFRQVLGHULQJDFDWDO\VWGHDFWLYDWLRQRI
L[ )LJXUH²%UHDNWKURXJKFXUYHVSHUIRUPHGLQWKHIL[HGEHGDGVRUSWLYHUHDFWRUDQGLQD VLQJOH60%5FROXPQIRUZDWHU'062DDQG*($'062EELQDU\PL[WXUHVDW . DQGIORZUDWHVRIDSSUR[LPDWHO\ P/ PLQ − ⋅ )LJXUH²([SHULPHQWDODQGWKHRUHWLFDO60%5FRQFHQWUDWLRQSURILOHVDWWKHF\FOLF VWHDG\VWDWHFRQVLGHULQJWKHFRUUHFWHGDGVRUSWLRQSDUDPHWHUVIRUWKHDJHG $PEHUO\VW
[ /LVWRI7DEOHV 7DEOH²5HIHUHQFHIXHOVFKDUDFWHULVWLFV 7DEOH²,QIOXHQFHRIEOHQGLQJJO\FHURODFHWDOVDQGUDSHVHHGPHWK\OHVWHUVZLWKGLHVHO RQSDUWLFOHPDWWHUDQG [ 12 HPLVVLRQV 7DEOH²(IIHFWRQSDUWLFOHVHPLVVLRQVRIWKHDGGLWLRQRI*($WRJDVRLO 7DEOH²/LWHUDWXUHUHYLHZRIFDWDO\VWVXVHGLQDFHWDOL]DWLRQUHDFWLRQV 7DEOH,RQ([FKDQJH5HVLQVWHVWHGLQFDWDO\VWVFUHHQLQJH[SHULPHQWV 7DEOH.LQHWLFH[SHULPHQWVRSHUDWLQJFRQGLWLRQV 7DEOH5HODWLYHPROHFXODUYROXPHDQGVXUIDFHDUHDRISXUHVSHFLHV81,)$& SDUDPHWHUV 7DEOH²%LQDU\LQWHUDFWLRQSDUDPHWHUVIRUWKH81,)$&JURXSVSUHVHQWHGLQ7DEOH 7DEOH²(TXLOLEULXPH[SHULPHQWVFRQGLWLRQVDQGUHVXOWV 3 EDU = DQG ZW RI $PEHUO\VWZHWXVHGLQDOOH[SHULPHQWV 7DEOH6WDQGDUGHQWKDOS\DQGIUHH*LEEVHQHUJ\RIIRUPDWLRQIRUDOOWKHVSHFLHV 7DEOH(IIHFWRIWKHDOGHK\GHFKDLQOHQJWKRQWKHHTXLOLEULXPFRQYHUVLRQRIWKH DFHWDOL]DWLRQRIJO\FHURODW . 7DEOH(VWLPDWHGNLQHWLFSDUDPHWHUVIRUWKH3+DQG/++:PRGHOVDQGUHVSHFWLYH REMHFWLYHIXQFWLRQYDOXHV 7DEOH.LQHWLFH[SHULPHQWVRSHUDWLQJFRQGLWLRQV 7DEOH²3ULPDU\OLVWRIVROYHQWV 7DEOH5DQNRIVROYHQWVE\SURFHVVSHUIRUPDQFHDQGSURFHVVLPSDFWEDVHGRQWKHLU SURSHUWLHV 7DEOH.LQHWLFSDUDPHWHUVHVWLPDWHGIRUWKHDFHWDOL]DWLRQRIJO\FHUROLQSUHVHQFHRI '062 7DEOH²&RUUHFWHGHVWLPDWLRQRIWKHNLQHWLFSDUDPHWHUVIRUWKHDFHWDOL]DWLRQRI JO\FHUROLQSUHVHQFHRI'062
[L 7DEOH²$PEHUO\VWZHWSK\VLFDOSURSHUWLHV 7DEOH²)L[HGEHGFROXPQSURSHUWLHV 7DEOH²%LQDU\EUHDNWKURXJKH[SHULPHQWDOFRQGLWLRQV 7DEOH²7HUQDU\EUHDNWKURXJKH[SHULPHQWDOFRQGLWLRQV 7DEOH7UDFHUH[SHULPHQWVUHVXOWV 7DEOH²*O\FHUROZDWHU*($DQG'062/DQJPXLUDGVRUSWLRQFRPSHWLWLYHSDUDPHWHUV RYHU$PEHUO\VW 7DEOH²$YHUDJH60%5FROXPQVSURSHUWLHV 7DEOH60%5RSHUDWLQJFRQGLWLRQV 7DEOH0DWKHPDWLFDOPRGHOIRUWKHGHVFULSWLRQRIWKHM WK IL[HGEHGFROXPQRIWKH 60%5ZLWK ∈ ª º ¬ ¼ F Q M 7DEOH60%5SHUIRUPDQFHSDUDPHWHUV 7DEOH%LQDU\EUHDNWKURXJKH[SHULPHQWDOFRQGLWLRQV
&KDSWHU ,QWURGXFWLRQ 7KHVLV)UDPHZRUNDQG3UHVHQWDWLRQ $WWKHSUHVHQWWLPHSHWUROHXPLVVWLOODWWKHFHQWUHRIHQHUJ\DQGWUDQVSRUWDWLRQIXHOV SURGXFWLRQDQGPRVWRIWKHFRXQWULHVZRUOGZLGHDUHGUDVWLFDOO\GHSHQGHQWRQWKLVVRXUFHRI HQHUJ\+RZHYHURYHUWKHODVWGHFDGHVWKHLQFUHDVLQJHQYLURQPHQWDOFRQFHUQVDORQJZLWK WKH DZDUHQHVV RI WKH GHFOLQH RI SHWUROHXP UHVHUYHV DQG LWV FRQVHTXHQW SULFH UDLVLQJ DQG PDUNHWLQVWDELOLW\KDYHEHHQSURPSWLQJWKHGHYHORSPHQWRIDOWHUQDWLYHVWRIRVVLOUHVRXUFHV DQGWKHLPSOHPHQWDWLRQRI´JUHHQHUµSROLFLHV6HYHUDOUHQHZDEOHHQHUJ\VRXUFHVVXFKDVVXQ ZLQG ZDYHV JHRWKHUPDO DQG ELRPDVV KDYH EHHQ LGHQWLILHG DV VXVWDLQDEOH VXEVWLWXWHV IRU SHWUROHXP<HWWKHVWDWHRIWKHDUWRIPRVWRIWKHWHFKQRORJLHVDVVRFLDWHGWRWKHVHUHVRXUFHV LV QRW VXIILFLHQWO\ DGYDQFHG IRU LWV SUHYDOHQFH SULPDULO\ GXH WR LWV UHVWULFWHG HFRQRPLF YLDELOLW\ %LRIXHOV GHULYHG IURP ELRPDVV RQ WKH RWKHU KDQG VHHP WR RYHUFRPH WKH LPSOLFDWLRQV EURXJKWE\WKHH[FHVVLYHXVHRIIRVVLOIXHOVEHLQJDVXVWDLQDEOHHQYLURQPHQWDOO\IULHQGO\DQG FRVWHIIHFWLYHDOWHUQDWLYH,QWKLVW\SHRIIXHOVFDQEHLQFOXGHGHWKDQRODQDOFRKROSURGXFHG IURP FRUQ RU VXJDUFDQH IRU LQVWDQFH ELRGLHVHO PRQRDON\O HVWHUV SURGXFHG WKURXJK WKH UHDFWLRQRIDYHJHWDEOHRLORUDQLPDOIDWZLWKDQDOFRKROVXFKDVPHWKDQRORUHWKDQRODQG ELRJDVPDLQO\REWDLQHGIURPGLJHVWHGRUJDQLFPDWHULDO ,QWKHIXWXUHDWUDQVLWLRQWRZDUGVDELREDVHGHFRQRP\LVH[SHFWHGLQZKLFKELRUHILQHU\ SURFHVVHV ZLOO KDYH D PDMRU UROH +RZHYHU FXUUHQW ELRUHILQHULHV DUH IRFXVHG LQ OLPLWHG IHHGVWRFNDQGSURFHVVLQJWHFKQRORJLHVSURGXFLQJH[FOXVLYHO\DELRIXHO7KHPDMRULW\RIWKH E\SURGXFWVDQGRWKHUFKHPLFDOVSURGXFHGLQWKHVHXQLWVDUHQHJOHFWHGZKLFKFRQVHTXHQWO\ OHDGV WR D GHFUHDVH RI WKH DGGHG YDOXH RI WKH ELRPDVV FKDLQ 5HJDUGLQJ WKH SUHYLRXVO\ PHQWLRQHGGUDZEDFNVD(XURSHDQFROODERUDWLYHSURMHFWZDVFUHDWHGXQGHUWKHGHVLJQDWLRQRI ´(852SHDQ PXOWLOHYHO LQWHJUDWHG %,25()LQHU\ GHVLJQ IRU VXVWDLQDEOH ELRPDVV SURFHVVLQJµ (XUR%LR5HI²SURMHFWZLWKLQZKLFKWKLVZRUNLVGHYHORSHG(XUR%LR5HILQYROYHVHQWLWLHV
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´/DERUDWRU\ RI 6HSDUDWLRQ DQG 5HDFWLRQ(QJLQHHULQJµ/65(RIWKH´)DFXOGDGHGH(QJHQKDULDGD8QLYHUVLGDGHGR3RUWRµ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·VOHDGLQJ SURGXFHU RI WKLV NLQG RI IXHOV DQG ZLWK WKH H[SHFWHG LQFUHDVH RI LWV PDUNHW JO\FHURO LV EHFRPLQJZLGHO\DYDLODEOHDWORZHUSULFHVWXUQLQJLWLQWRDQLQWHUHVWLQJUDZPDWHULDOIRUWKH V\QWKHVLV RI QHZ DGGHG YDOXH SURGXFWV VLQFH LWV FRQYHQWLRQDO PDUNHW FDQ·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²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
6 7$7(2)7+( $ 57 )LJXUH ²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ilva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²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− ⋅ NPRO ZDVREVHUYHG7KLVYDOXHLVLQDJUHHPHQW ZLWKWKDWSXEOLVKHGE\WKHVDPHDXWKRUVIRUWKHFRQGHQVDWLRQRIJO\FHUROZLWKIRUPDOGHK\GH − ⋅ NPRO DQGZLWKWKHSXEOLVKHGE\1DQGDHWDOIRUWKHFRQGHQVDWLRQRIJO\FHUROZLWK DFHWRQH − ⋅ NPRO $ ILQDO UHPDUN VKRXOG EH OHIW WR WKH IRUPDWLRQ RI WULR[DQH DV D VHFRQGDU\ SURGXFW ZKHQ DFHWDOGHK\GH LV SUHVHQW LQ H[FHVV IRUPHG DIWHU JO\FHURO EHLQJ FRPSOHWHO\FRQVXPHG 7UDQVDFHWDOL]DWLRQ5HDFWLRQ ,QWKHSUHVHQFHRIDQDFLGFDWDO\VWJO\FHUROUHDFWVZLWKDQDFHWDOH[RWKHUPLFDOO\WRIRUP *($LVRPHULFPL[WXUHSUHVHQWHGLQ)LJXUHDQGWKHFRUUHVSRQGLQJDOFRKROVDFFRUGLQJWR HTXDWLRQ $FHWDO *O\FHURO *($ PHPEHUHG ULQJLVRPHU *($ PHPEHUHG ULQJLVRPHU $OFRKROV
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
6 7$7(2)7+( $ 57 )LJXUH ²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− ⋅ NPRO ZDV HVWLPDWHG 7KH PRVW VLJQLILFDQW FRQFOXVLRQ WKDW FDQ EH ZLWKGUDZQIURPWKHVHUHVXOWVLVWKHH[RWKHUPLFEHKDYLRXURIWKHWUDQVDFHWDOL]DWLRQDVLWLV REVHUYHG IRU DFHWDOL]DWLRQ UHDFWLRQV DVZHOODQGLWV KLJKYDOXHRIHTXLOLEULXP FRQVWDQWDV SUHYLRXVO\PHQWLRQHG ,Q WKH VDPH SDSHU WKH DXWKRUV VWXG\ WKH NLQHWLF EHKDYLRXU RI WKH UHDFWLRQ LQ WKH SUHVHQFHRI$PEHUO\VW7KHH[LVWHQFHRIPLOGLQWUDSDUWLFOHPDVVWUDQVIHUUHVLVWDQFHVZDV
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 7DEOH²5HIHUHQFHIXHOVFKDUDFWHULVWLFV 3URSHUWLHV 5HIHUHQFH)XHO 5HIHUHQFH)XHO 'HQVLW\NJͼP &HWDQH1XPEHU 6XOSKXU&RQWHQWSSP 2[\JHQ &DUERQ ,QLWLDO%RLOLQJ3RLQW. )LQDO%RLOLQJ3RLQW. $URPDWLFV :KHQXVHGZLWKRXWDQ\DGGLWLYHUHIHUHQFHIXHOVDQGSUHVHQWHGSDUWLFOHVHPLVVLRQVRI DSSUR[LPDWHO\ − ⋅ J NP DQG − ⋅ J NP ZKLOH WKH SROOXWDQWV HPLVVLRQV QDPHO\ [ 12 ZHUHDSSUR[LPDWHO\ − ⋅ J NP DQG − ⋅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
6 7$7(2)7+( $ 57 7DEOH²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²(IIHFWRQSDUWLFOHVHPLVVLRQVRIWKHDGGLWLRQRI*($WRJDVRLO )XHO 3DUWLFOHHPLVVLRQVJͼ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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 WKH VLPXOWDQHRXV DGGLWLRQ RI DQ DOFRKRO XVXDOO\ HWKDQRO WR WKH JDVROLQH ,Q IDFW WKLV SURFHGXUHQRWRQO\HOLPLQDWHGWKHPLVFLELOLW\SUREOHPVRIDFHWDOVDVLWKDVSURYHGWREHDQ HIILFLHQW SURFHVV IRU LQFUHDVLQJ WKH RFWDQH QXPEHU RI WKH IXHO *($ ZDV RQH RI WKH FRPSRXQGVHYDOXDWHG$QDPRXQWRIRIWKLVDFHWDOSOXVRIHWKDQRODOOSHUFHQWDJHV E\ ZHLJKW ZHUH DGGHG WR D PRGHO PL[WXUH RI LVRRFWDQHQKHSWDQH OHDGLQJ WR D VLJQLILFDQW LQFUHDVH RI XQLWV LQ WKH RFWDQH QXPEHU RI WKH ILQDO IXHO FRPSRVLWLRQ )XUWKHUPRUH WKLV ZRUN DOVR PHQWLRQV WKDW WKH XVH RI WKHVH PL[WXUHV RI F\FOLF DFHWDOV DQG DOFRKROVDUHDEOHWRHQKDQFHWKHVWDELOLW\RIWKHIXHOKDYLQJDSRVLWLYHLPSDFWRQLQWHUQDO FRPEXVWLRQHQJLQHV 7KHQRWRULRXVUHVXOWVIURPWKHXVHRIF\FOLFDFHWDOVRIJO\FHURODVHQYLURQPHQWDOIULHQGO\ DGGLWLYHV SURPSWHG WKH GHYHORSPHQW RI SURFHVVHV WKDW LQWHJUDWH WKH SURGXFWLRQ RI WKHVH FRPSRXQGVVLPXOWDQHRXVO\WRELRGLHVHOSURGXFWLRQDOORZLQJWKHUHFRYHU\RIWKHJO\FHURODQG LQFUHDVLQJWKHRYHUDOOSURFHVV\LHOG$QH[DPSOHRIWKLVLVWKHSDWHQWVXEPLWWHGE\0LOOHUHW DO SUHYLRXVO\ GLVFXVVHG 7KH SURFHVV FRQVLVWV RQD WUDQVHVWHULILFDWLRQXQLW WR SURGXFH DQ HTXLOLEULXPPL[WXUHRIELRGLHVHOJO\FHURODQGXQUHDFWHGDOFRKRODQGWULJO\FHULGHVZKLOHLQD SDUDOOHOXQLWWKHUDZPDWHULDOIRUWKHF\FOLFDFHWDODOGHK\GHRUDFHWDOLVEHLQJV\QWKHVLVHG %RWKRXWOHWVWUHDPVRIWKHVHXQLWVDUHIHGWRDGLVWLOODWLRQFROXPQ$ELRGLHVHOFRQWDLQLQJDQ DFHWDOGHULYHGIURPJO\FHUROLVREWDLQHGDVILQDOSURGXFW,QWKLVZRUNDXWKRUVGHVFULEHWKH SDUWLFXODUSURFHVVIRUWKHSURGXFWLRQRI*($DVDGGLWLYHIRUWKHELRGLHVHO$QRWKHUH[DPSOHRI LQWHJUDWHGSURGXFWLRQRIELRGLHVHODQGWKHUHVSHFWLYHF\FOLFDFHWDODGGLWLYHZDVUHSRUWHGLQ +LOOLRQHWDOSDWHQW $VSHFLILFKHWHURJHQHRXVFDWDO\VWFRQVWLWXWHGE\DQR[LGHDQGRUDQ DOXPLQLXPR[LGHRIPHWDOVVXFKDV]LQFWLWDQLXP]LUFRQLDRUELVPXWKIRULQVWDQFHVKRXOGEH XVHG WR SURPRWH WKH WUDQVHVWHULILFDWLRQ UHDFWLRQ IRU WKH SURGXFWLRQ RI D FRQYHQWLRQDO ELRGLHVHODQGIUHHJO\FHURODVLPSXULW\7KLVJO\FHUROFRXOGWKHQEHXVHGIRUWKHV\QWKHVLVRI F\FOLFDFHWDOVDGGLWLYHVWKURXJKUHDFWLRQZLWKWKHFRUUHVSRQGHQWDOGHK\GHDQGWKHSURGXFW LVILQDOO\LQWURGXFHGLQELRGLHVHO -HW)XHO$GGLWLYH 7KHORZWHPSHUDWXUHVIRXQGDWWKHKLJKDOWLWXGHVDWZKLFKDLUFUDIWVIO\PLJKWLQGXFHWKH IRUPDWLRQRILFHIURPWKHZDWHUGLVVROYHGLQWKHMHWIXHOZKHQLWLVORDGHGRQWRWKHDLUFUDIW ZKLFKVHSDUDWHVIURPWKHIXHODVLWVWHPSHUDWXUHGURSV7KHSUHVHQFHRILFHFU\VWDOVLQWKH IXHO OLQHV FDQ FDXVH VHYHUH SUREOHPV WKURXJK WKH UHGXFWLRQ RI IXHO IORZ WR WKH HQJLQH $OWKRXJK PRVW FRPPHUFLDO DLUFUDIWV KDYH KHDWHUV RQ WKHLU PDLQ ILOWHUV SUHYHQWLQJ LFH GHSRVLWLQJE\PHOWLQJLWPDQ\PLOLWDU\DLUFUDIWGRQRWKDYHWKRVHKHDWHUVDQGWKHUHIRUHWKH XVHRIDYLDWLRQIXHODGGLWLYHVWRDYRLGWKLVSUREOHPEHFRPHVQHFHVVDU\7KHVHDGGLWLYHVDUH FRPPRQO\ UHIHUUHG WR DV )XHO 6\VWHP ,FLQJ ,QKLELWRUV )6,, DQG FRQVLVW RQ FKHPLFDO FRPSRXQGVWKDWGLVVROYHZLWKZDWHUSUHIHUHQWLDOO\RYHUWKHMHWIXHOORZHULQJVLJQLILFDQWO\LWV IUHH]LQJSRLQWVRWKDWQRLFHFU\VWDOVDUHIRUPHG7KHVHFRPSRXQGVDUHDGGHGLQYHU\VPDOO
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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH ²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·VODZZLOOUHVXOWLQDVKLIWLQJRIWKHUHDFWLRQIDYRXULQJSURGXFWVIRUPDWLRQ DQG WKHUHIRUH LQFUHDVLQJ FRQYHUVLRQ 7KLV IDFW DOORZV WKLV VRUW RI XQLWV WR EH DEOH WR RYHUFRPHWKHUPRG\QDPLFOLPLWDWLRQVWKDWDUHDVVRFLDWHGWRDQXPEHURIUHDFWLRQV 7KH SRWHQWLDO WR UHGXFH FDSLWDO LQYHVWPHQW LV JHQHUDOO\ HQGRUVHG WR PXOWLIXQFWLRQDO UHDFWRUVVLQFHLQVWHDGRIXVLQJDWOHDVWWZRXQLWVWRREWDLQWKHILQDOSURGXFWWKHLQWHJUDWHG SURFHVVZLOORQO\UHTXLUHRQH )XUWKHUPRUHDPRQJWKHDGYDQWDJHVRIK\EULGUHDFWRUVWKH ϮϯϬ ϮϰϬ ϮϱϬ ϮϲϬ ϮϳϬ ϮϴϬ ϮϵϬ ϯϬϬ Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ d;<Ϳ dŝŵĞ;ŵŝŶͿ ϮͲŵĞƚŚLJůͲϭϯͲĚŝŽdžŽůĂŶĞͲϰͲŵĞƚŚĂŶŽů ĚŝĞƚŚLJůĞŶĞŐůLJĐŽůŵŽŶŽŵĞƚŚLJůĞŚƚĞƌ ϭϯͲĚŝŽdžŽůĂŶĞͲϰͲŵĞƚŚĂŶŽů ĚŝƉƌŽƉLJůĞŶĞŐůLJĐŽů
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´6RUEH[ µ SURFHVV WKH 60% KDV EHHQ ODUJHO\ DSSOLHGLQWKHSHWURFKHPLFDOILHOGIRUWKHSXULILFDWLRQRIS[\OHQHLQWKH´3DUH[ µSURFHVV RUIRUWKHVHSDUDWLRQRIROHILQVIURPSDUDIILQVLQWKH´2OH[ µ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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 VROLGLVVLPXODWHGE\WKHV\QFKURQL]HGSHULRGLFVKLIWLQJRILQOHWVDQGRXWOHWVIRURQHFROXPQ GLVWDQFHLQWKHGLUHFWLRQRIWKHIOXLGIORZ*HQHUDOO\WKHUHDUHWZRLQOHWVWUHDPVIHHGDQG GHVRUEHQWDQGWZRRXWOHWVWUHDPVH[WUDFWDQGUDIILQDWH7KHUHDFWDQWVDUHLQWURGXFHGLQWKH XQLWWKURXJKWKHIHHGVWUHDPZKLOHWKHPRVWDQGOHDVWDGVRUEHGVSHFLHVDUHFROOHFWHGLQWKH H[WUDFWDQGUDIILQDWHUHVSHFWLYHO\7KHSRVLWLRQRIWKHLQOHWDQGRXWOHWVWUHDPVGHILQHVWKH GLYLVLRQRIWKHXQLWLQIRXUVHFWLRQV •6HFWLRQ , EHWZHHQ GHVRUEHQW DQG H[WUDFW SRUWV WKH PRUH VWURQJO\ DGVRUEHG SURGXFW GHVRUEV IURP WKH VROLG UHJHQHUDWLQJ LW )RU WKDW SXUSRVH WKH KLJKHVW IORZUDWHZLWKLQWKHXQLWLVUHTXLUHGLQWKLVVHFWLRQ •6HFWLRQ,,EHWZHHQH[WUDFWDQGIHHGSRUWVUHDFWLRQWDNHVSODFHDQGWKHPRUH VWURQJO\DGVRUEHGSURGXFWLVWUDQVSRUWHGZLWKWKHVROLGSKDVHWRZDUGVWKHH[WUDFW SRUWZKHUHLWLVZLWKGUDZQ7KHOHVVVWURQJO\DGVRUEHGSURGXFWLVWUDQVSRUWHGZLWK WKHOLTXLGLQGLUHFWLRQRIWKHUDIILQDWHSRUW •6HFWLRQ ,,, EHWZHHQ IHHG DQG UDIILQDWH SRUWV UHDFWLRQ DQG VHSDUDWLRQ RFFXU LGHQWLFDOO\ WR 6HFWLRQ ,, KRZHYHU DQ KLJKHU FRQFHQWUDWLRQ RI WKH OHVV DGVRUEHG SURGXFWLVREVHUYHGZKLFKLVFROOHFWHGLQWKHUDIILQDWHVWUHDP •6HFWLRQ ,9 EHWZHHQ UDIILQDWH DQG GHVRUEHQW SRUWV DGVRUSWLRQ RI WKH OHVV UHWDLQHG SURGXFW RFFXUV OHDGLQJ WR WKH UHJHQHUDWLRQ RI WKH GHVRUEHQW ZKLFK LV UHF\FOHGWR6HFWLRQ, $GHVFULSWLYHVFKHPHRIWKH70%5DQGWKH60%5LVSUHVHQWHGLQ)LJXUH D E )LJXUH ² 6FKHPHRID 70%5DDQGD 60%5 E XQLW 7KH GLIIHUHQFHV LQ WKH FRQFHQWUDWLRQ SURILOHV RI HDFK FRPSRXQG ZLWKLQ WKH XQLW DV D FRQVHTXHQFH RI WKH GLIIHUHQFHV LQ WKH DGVRUEHQW VHOHFWLYLW\ WRZDUGV HDFK RQH DUH WKH H[SODQDWLRQIRUWKH60%5VHSDUDWLRQDQGHTXLOLEULXPGLVSODFHPHQWFDSDFLWLHV+RZHYHUDQ
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− ⋅ ZKLOHWKHUDIILQDWHZDVFROOHFWHGDW P/ PLQ − ⋅ 7KHVH H[SHULPHQWDO FRQGLWLRQV DOORZHG DQ DFHWDOGHK\GH FRQYHUVLRQ RI DSSUR[LPDWHO\ DQG D UDIILQDWH VWUHDP SXULW\ RI 7KH SURGXFWLYLW\ DQG GHVRUSWLRQ FRQVXPSWLRQ ZHUH − − ⋅ ⋅ 3URG $GV NJ / GD\ DQG 'HV 3URG / NJ − ⋅ UHVSHFWLYHO\ 6LPXODWLRQ VWXGLHVGHPRQVWUDWHGWKDWLWZRXOGEHSRVVLEOHWRLPSURYHWKHXQLWSHUIRUPDQFH$PD[LPXP SURGXFWLYLW\RI − − ⋅ ⋅ 3URG $GV NJ / GD\ ZLWKDUDIILQDWHSXULW\RIZDVUHSRUWHGWRJHWKHU ZLWKDGHVRUEHQWFRQVXPSWLRQRI 'HV 3URG / NJ − ⋅ *LYHQWKHSRVLWLYHUHVXOWVREWDLQHGIRUWKH'((SURGXFWLRQLQWKH60%5WKHV\QWKHVLVRI GLPHWKR[\HWKDQH DQG GLEXWKR[\HWKDQH ZHUH DOVR VWXGLHG )RU WKHVH SURFHVVHVWKH UHVSHFWLYH DOFRKRO ZDV XVHG DV GHVRUEHQW DQG UHDFWHG ZLWKDFHWDOGHK\GHLQ WKH SUHVHQFH RI $PEHUO\VW $ SDUWLFXODUO\ KLJK SURGXFWLYLW\ ZDV REWDLQHG IRU GLEXWKR[\HWKDQH7KHRSWLPL]HGYDOXHDFKLHYHGE\VLPXODWLRQZDV − − ⋅ ⋅ 3URG $GV NJ / GD\ &RQFOXVLRQ 7KHELEOLRJUDSKLFUHVHDUFKSUHVHQWHGLQWKLV&KDSWHUDOORZHGWKHLGHQWLILFDWLRQRI*($DV DKLJKDGGHGYDOXHSURGXFW7KHHQYLURQPHQWDOEHQHILWVRIWKLVDFHWDODUHQRWRQO\UHODWHG
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´JUHHQHUµ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|EORP%LRIXHOV²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²S 3UDPDQLN 7 DQG 6 7ULSDWKL %LRGLHVHO &OHDQ IXHO RI WKH IXWXUH 1HZ SURFHVVLQJ WHFKQRORJLHV XQFRYHU PHDQV WR SURGXFH ORZVXOIXU ELRPDVVEDVHG GLHVHO +\GURFDUERQ3URFHVVLQJS 5LEHLUR 10 $& 3LQWR &0 4XLQWHOOD *2 GD 5RFKD /6* 7HL[HLUD //1 *XDULHLUR 0 GR &DUPR 5DQJHO 0&& 9HORVR 0-& 5H]HQGH 5 6HUSD GD &UX] $0GH2OLYHLUD($7RUUHVDQG-%GH$QGUDGH7KH5ROHRI$GGLWLYHVIRU'LHVHO DQG 'LHVHO %OHQGHG (WKDQRO RU %LRGLHVHO )XHOV࣯ $ 5HYLHZ (QHUJ\ )XHOV S 6FKDUOHPDQQ -3: DQG :) /DXUDQFH (QYLURQPHQWDO VFLHQFH +RZ JUHHQ DUH ELRIXHOV"6FLHQFHS 8OJLDWL 6 $ &RPSUHKHQVLYH (QHUJ\ DQG (FRQRPLF $VVHVVPHQW RI %LRIXHOV :KHQ ´*UHHQµ,V1RW(QRXJK&ULWLFDO5HYLHZVLQ3ODQW6FLHQFHVS +LOO-(1HOVRQ'7LOPDQ63RODVN\DQG'7LIIDQ\(QYLURQPHQWDOHFRQRPLF DQG HQHUJHWLF FRVWV DQG EHQHILWV RI ELRGLHVHO DQG HWKDQRO ELRIXHOV 3URFHHGLQJV RI WKH1DWLRQDO$FDGHP\RI6FLHQFHVS .HOORZD\ $ DQG 3 'DRXWLGLV 3URFHVV 6\QWKHVLV RI %LRUHILQHULHV 2SWLPL]DWLRQ RI %LRPDVV &RQYHUVLRQ WR )XHOV DQG &KHPLFDOV ,QGXVWULDO (QJLQHHULQJ &KHPLVWU\ 5HVHDUFK
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
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 PDMRUGUDZEDFNRIWKHDFHWDOL]DWLRQUHDFWLRQVLVWKHIRUPDWLRQRIZDWHUZKLFKLVXQGHVLUDEOH LQ VRPH *($ ILQDO DSSOLFDWLRQV LQFOXGLQJ LWV XVH DV IXHO DGGLWLYH 1HYHUWKHOHVV ZDWHUIUHH *($FDQEHREWDLQHGE\WKHXVHRIDQLQWHJUDWHGUHDFWLRQî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²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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 $FLG&DWDO\VLV &DWDO\VW &RQGLWLRQV 7LPHK <LHOG =HROLWHV +6= 5HDFWDQWV6WDQRORQHHWK\OHQHJO\FROPRO &DWDO\VWPP 7HPSHUDWXUH1$ 6ROYHQW7ROXHQHPROPRO =60 5HDFWDQWVJO\FHUROIRUPDOGHK\GHPRO &DWDO\VWPP 7HPSHUDWXUH. 6ROYHQW6ROYHQWIUHH 6LOLFDEDVHG 0HVRSRURXV 0DWHULDOV 0R2 6L2 5HDFWDQWVQKHSWDQDOJO\FHUROPRO &DWDO\VWPP 7HPSHUDWXUH. 6ROYHQW7ROXHQHPROPRO 0&0 5HDFWDQWVEHQ]DOGHK\GHPHWKDQROPRO &DWDO\VWPP 5RRPWHPSHUDWXUH 6ROYHQW6ROYHQWIUHH /HZLVDFLG $X&O 5HDFWDQWVQKHSWDQDOJO\FHURO &DWDO\VWPROPRO 7HPSHUDWXUH. 6ROYHQWGLR[DQHPROPRO ,RQLFOLTXLG >+PLP@ 3: 2 5HDFWDQWVSURSDQDOJO\FRO &DWDO\VWPROPRO 7HPSHUDWXUH1$ 6ROYHQW7ROXHQHPP &OD\0LQHUDOV 0RQWPRULOORQLWH . 5HDFWDQWVEHQ]DOGHK\GHJO\FHUROPRO &DWDO\VWPP 7HPSHUDWXUH1$ 6ROYHQW&KORURIRUPPROPRO 7KHEHQHILWVRIKHWHURJHQHRXVFDWDO\VLVRYHUKRPRJHQHRXVFDWDO\VLVDUHZHOONQRZQDQG DUHPDLQO\UHODWHGZLWKWKHHDVHRIVHSDUDWLRQDQG SXULILFDWLRQRIWKHGHVLUHGSURGXFWDQG WKH DEVHQFH RI WKH QHHG IRU QHXWUDOL]DWLRQ VWHSV $PRQJ WKH KHWHURJHQHRXV FDWDO\VWV PHQWLRQHGDOXPLQRVLOLFDWHVVXFKDV]HROLWHVSUHVHQWJRRGSHUIRUPDQFHVKRZHYHUDFLGLRQ H[FKDQJH UHVLQV KDYH GHPRQVWUDWHG WR EH SDUWLFXODUO\ HIIHFWLYH IRU WKLV W\SH RI UHDFWLRQ DFKLHYLQJ KLJKHU \LHOGV DSSUR[LPDWHO\ LQ VKRUW SHULRGV RI WLPH )XUWKHUPRUH WKHVH W\SHRIFDWDO\VWVKDYHEHHQVSHFLILFDOO\DSSOLHGLQWKHUHDFWLRQRIJO\FHUROZLWKVHYHUDOOLQHDU FKDLQDOGHK\GHV ZLWKFRQVLGHUDEOHVXFFHVV 7KHNLQHWLFVRIDFHWDOL]DWLRQDQGWUDQVDFHWDOL]DWLRQUHDFWLRQVIRUWKHV\QWKHVLVRIJO\FHURO DFHWDOV FDWDO\VHG E\ LRQ H[FKDQJH UHVLQV KDV EHHQ GHVFULEHG E\ WKH SVHXGRKRPRJHQHRXV
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 UHDFWLRQUDWHODZLQPRVWRIWKHUHSRUWHGZRUNV 2QWKHRWKHUKDQGWKHIRUPDWLRQRI JO\FHURO NHWDOV IRU LQVWDQFH WKURXJK WKH UHDFWLRQ EHWZHHQ JO\FHURO DQG DFHWRQH ZDV GHVFULEHG E\ D /DQJPXLU+LQVKHOZRRG+RXJHQ:DWVRQ EDVHG PRGHO +RZHYHU VLPLODU UHDFWLRQ DFWLYDWLRQ HQHUJLHV ZHUH HVWLPDWHG IRU DOO SUHYLRXVO\ FLWHG ZRUNV ZLWK YDOXHV FRPSULVHGEHWZHHQ NPRO − ⋅DQG NPRO − ⋅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î+LQVKHOZRRGî+RXJHQî:DWVRQUHDFWLRQUDWHODZVZHUHDVVHVVHGFRQVLGHULQJWKH HIIHFWRIWKHUHDFWLRQVSHFLHVGLIIXVLRQPHFKDQLVPVLQVLGHWKHFDWDO\VWSDUWLFOHV ([SHULPHQWDO'HVFULSWLRQ &KHPLFDOVDQG&DWDO\VWV 7KHFKHPLFDOVXVHGZHUHSURSDQRO!EXWDQRO!DFHWDOGHK\GH! DQGJO\FHURO!LQZDWHUIURP6LJPD$OGULFK'RUVHW8. 6HYHUDO FRPPHUFLDO VWURQJDFLG LRQH[FKDQJH UHVLQV 5RKP +DDV ZHUH WHVWHG DV FDWDO\VWV7DEOHSUHVHQWVWKHLUEULHIFKDUDFWHUL]DWLRQ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 7DEOH,RQ([FKDQJH5HVLQVWHVWHGLQFDWDO\VWVFUHHQLQJH[SHULPHQWV ,RQH[FKDQJH UHVLQ 7\SH 3K\VLFDO )RUP 3DUWLFOH6L]H PP ,RQ([FKDQJH &DSDFLW\HTNJ 6XUIDFH $UHDP $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV ² $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV ² $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV 1$ $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV 1$ 1$ 1$ $PEHUO\VW:HW6WURQJDFLG 2SDTXH EHDGV $PEHUO\VW&+ :HW6WURQJDFLG 2SDTXH EHDGV ²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î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|QLJVKRIHQ*HUPDQ\7KHSUHVVXUHZDVVHW WR EDU WRNHHSWKHUHDFWLRQPL[WXUHLQWKHOLTXLGSKDVH
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH 6FKHPHRIWKHVHW XSXVHGIRUNLQHWLFH[SHULPHQWV 5HDFWLRQ.LQHWLFV 7KHNLQHWLFVWXGLHVZHUHFDUULHGRXWLQWKHUHDFWLRQVHWXSSUHVHQWHGLQ)LJXUH7KH HIIHFWV RI SDUDPHWHUV VXFK DV VWLUULQJ VSHHG USP î USP FDWDO\VW DYHUDJH SDUWLFOH GLDPHWHU P µ DQG P µ DQGORDGLQJ ZW DQG ZW RIWKHWRWDOPDVVRIWKH UHDFWLRQPHGLXPWHPSHUDWXUH . î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ù PP LGILOPWKLFNQHVVRI P µ DQG TXDQWLILHG E\ D WKHUPDO FRQGXFWLYLW\ GHWHFWRU +HOLXP 1 ZDV XVHG DV WKH FDUULHU JDV DW D IORZ UDWH RI P/ PLQ − ⋅ 7KH WHPSHUDWXUHV RI WKH LQMHFWRU DQG WKHUPDO FRQGXFWLYLW\GHWHFWRUZHUHVHWWR . 7KHLQLWLDOFROXPQWHPSHUDWXUHZDV . IRU PLQ WKH WHPSHUDWXUH ZDV WKHQ LQFUHDVHG DW . PLQ − ⋅ WR . DQG VXEVHTXHQWO\ KHOG FRQVWDQWIRUWKHIROORZLQJ PLQ 7KHUPRG\QDPLF(TXLOLEULXP &RQVLGHULQJ WKH JOREDO H[SUHVVLRQ IRU WKH QRQLGHDO OLTXLGSKDVH UHDFWLRQ EHWZHHQ DFHWDOGHK\GHDQGJO\FHUROSUHVHQWHGLQHTXDWLRQWKHFKHPLFDOHTXLOLEULXPFRQVWDQWIRU WKLV UHDFWLRQ HT . FDQ EH H[SUHVVHG DV D IXQFWLRQ RI WKH DFWLYLWLHV RI ERWK UHDFWDQWV DQG SURGXFWVDFFRUGLQJWRHTXDWLRQ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 i GEA W GEA W GEA W eq i i Ac Gly Ac Gly Ac Gly a a x x K a a a x x ν γ γ γ γ = = = ∏ ZKHUH L D LVWKHDFWLYLW\RIFRPSRXQG L L ν LVWKHVWRLFKLRPHWULFFRHIILFLHQWRIFRPSRXQG L LQWKHUHDFWLRQ L [ LVWKHPRODUIUDFWLRQRIFRPSRXQG L DQG L γ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ν νν ν L 5 N 4 N $FHWDOGHK\GH &+ FKDLQHQGJURXS +&2 *O\FHURO &+ FKDLQPLGGOHJURXS &+FKDLQPLGGOHJURXS 2+ :DWHU + 2 *($ &+ FKDLQHQGJURXS &+ FKDLQPLGGOHJURXS &+FKDLQPLGGOHJURXS 2+ &+ 2 &+2 7DEOH²%LQDU\LQWHUDFWLRQSDUDPHWHUVIRUWKH81,)$&JURXSVSUHVHQWHGLQ7DEOH D PN
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∆ DQGWHPSHUDWXUH . DFFRUGLQJWRHTXDWLRQ 0 exp ν § · ∆ = − = ¨ ¸ © ¹ ∏ i eq i i G K a RT ZKHUH 5 LVWKHLGHDOJDVFRQVWDQW)XUWKHUPRUHHTXDWLRQGHVFULEHVWKHUHODWLRQVKLS EHWZHHQ WKH UHDFWLRQ VWDQGDUG *LEEV IUHH HQHUJ\ ZLWK WKH UHDFWLRQ VWDQGDUG HQWKDOS\ DQG HQWURS\ + ∆ DQG 6 ∆ UHVSHFWLYHO\ 0 0 0 G H T S ∆ = ∆ − ∆ :LWK WKH SXUSRVH RI HYDOXDWLQJ WKH FKHPLFDO HTXLOLEULXP FRQVWDQW IRU WKH V\QWKHVLV RI *($VHYHUDOH[SHULPHQWVZHUHSHUIRUPHGUHDFWLQJJO\FHURODQGDFHWDOGHK\GHZLWKGLIIHUHQW LQLWLDO PRODU UDWLRV DW YDULRXV WHPSHUDWXUHV DQG WKH UHDFWLRQ HTXLOLEULXP FRPSRVLWLRQ RI HDFKFRPSRXQGZDVPHDVXUHG7KHUHVXOWVDUHVKRZQLQ7DEOH 7DEOH²(TXLOLEULXPH[SHULPHQWVFRQGLWLRQVDQGUHVXOWV 3 EDU = DQG ZW RI $PEHUO\VWZHWXVHGLQDOOH[SHULPHQWV U $FHW*O\ 7. /LPLWLQJ5HDFWDQW &RQYHUVLRQ L L L [ ν νν ν ∏ ∏∏ ∏ L L L ν νν ν γ γγ γ ∏ ∏∏ ∏ . HT
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH ²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µ DQG P µ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Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ ϰϱϬƌƉŵ ϯϬϬƌƉŵ ϮϱϬƌƉŵ
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ε ε = ∂ ∂§ · − = − ¨ ¸ ∂ ∂ © ¹ P p i b i b eff i p b r R C CD t R r ( ) , , 2 , 2 11 p i p i p eff i p i s C C D r t r r r ε ε ν ρ ∂ ∂ § · ∂ = + − ℜ ¨ ¸ ∂ ∂ ∂ © ¹ ,QWKHVHHTXDWLRQVWKHLQGH[ L UHIHUVWRDUHDFWLRQVSHFLHVDFHWDOGHK\GHJO\FHURO*($ RU ZDWHU E L & DQG S L & UHSUHVHQW WKH PRODU FRQFHQWUDWLRQV HYDOXDWHG LQ WKH EXON DQG LQWUDSDUWLFOH IOXLG UHVSHFWLYHO\ S 5 UHSUHVHQWV WKH FDWDO\VW SDUWLFOH UDGLXV HII L ' LV WKH HIIHFWLYHGLIIXVLRQFRHIILFLHQW E ε DQG S ε DUHWKHEXONDQGWKHFDWDO\VWSDUWLFOHSRURVLWLHV UHVSHFWLYHO\IRUWKHVHWH[SHULPHQWVSHUIRUPHGWKHEXONSRURVLW\YDOXHUDQJHGIURPWR ρ V LVWKHVROLGGHQVLW\ L ν LVWKHVWRLFKLRPHWULFFRHIILFLHQWDQG ℜ LVWKHUHDFWLRQ UDWHEDVHGRQWKHORFDOLQWUDSDUWLFOH FRPSRVLWLRQ7KHPHWKRGIRU FRPSXWLQJ WKHHIIHFWLYH GLIIXVLRQ FRHIILFLHQWV DQG WKH SK\VLFDO SURSHUWLHV RI WKH UHDFWLRQ VSHFLHV UHTXLUHG IRU WKDW SXUSRVHDUHGHVFULEHGLQ$SSHQGL[ )RUWKLVPRGHORQHFDQDVVXPHWKHIROORZLQJLQLWLDOFRQGLWLRQV 0 , , 0 b i b i t C C = → = 0 , , 0 p i p i t C C = → =
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 DQGERXQGDU\FRQGLWLRQV , 0 0 p i C r t ∂ = → = ∂ , , = = → = p p b i p i r R r R C C 7KHUHDFWLRQUDWHZDVGHVFULEHGE\WZRGLIIHUHQWPRGHOVSVHXGRKRPRJHQHRXV3+DQG /DQJPXLUî+LQVKHOZRRGî+RXJHQî:DWVRQ /++: 7KH 3+ PRGHO FRQVLGHUV D UHYHUVLEOH UHDFWLRQRIILUVWRUGHULQHDFKVSHFLHVDQGFDQEHH[SUHVVHGLQWHUPVRIDFWLYLWLHVDVVKRZQLQ HTXDWLRQ § · ℜ = − ¨ ¸ ¨ ¸ © ¹ GEA W c Ac Gly eq a a k a a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§ · − ¨ ¸ ¨ ¸ © ¹ ℜ = + GEA W Ac Gly eq c s W W a a a a K k K a ZKHUH V : . UHSUHVHQWVWKHZDWHUDGVRUSWLRQHTXLOLEULXPFRQVWDQW 7KHWHPSHUDWXUHGHSHQGHQFHRIWKHUHDFWLRQNLQHWLFDQGHTXLOLEULXPDGVRUSWLRQFRQVWDQWV LV H[SUHVVHG E\ WKH $UUKHQLXV HTXDWLRQ DQG 9DQ·W +RII HTXDWLRQ HTXDWLRQV UHVSHFWLYHO\
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 0exp a c c E k k RT § · = − ¨ ¸ © ¹ 0 , , , exp ∆ § · = − ¨ ¸ © ¹ s W s W s W H K K RT 7KH YDULDEOHV F N DQG : V . UHSUHVHQW WKH $UUKHQLXV DQG 9DQ·W +RII HTXDWLRQV SUH H[SRQHQWLDO IDFWRUV UHVSHFWLYHO\ ZKLOH D ( UHSUHVHQWV WKH UHDFWLRQ DFWLYDWLRQ HQHUJ\ DQG : V +∆ UHSUHVHQWVZDWHUDGVRUSWLRQHQWKDOS\ 7KHFRPPHUFLDOVRIWZDUHJ35206*HQHUDO3URFHVV0RGHOOLQJ6\VWHPYHUVLRQZDV XVHGWRVROYHWKHPRGHOHTXDWLRQVIURPHTXDWLRQWRDQGWRHVWLPDWHWKHYDOXHVRI WKHXQNQRZQSDUDPHWHUV D ( DQG F N IRUWKH3+PRGHODQG D ( F N : V +∆ DQG : V . IRU WKH /++: PRGHO 7KHSDUWLDO GLIIHUHQWLDO HTXDWLRQV ZHUH WUHDWHG XVLQJ J35206 QXPHULFDO VROYHU '$62/9 GLVFUHWLVLQJ WKH UDGLDO GRPDLQ WKURXJK D FHQWUHG ILQLWHHOHPHQW PHWKRG RI VHFRQG RUGHU DQG XVLQJ QRQXQLIRUP GLVFUHWLVDWLRQ LQWHUYDOV 7KH HVWLPDWLRQ RI WKH SDUDPHWHUV IRU WKH SURSRVHG UHDFWLRQ UDWH PRGHOV ZDV FDUULHG RXW XVLQJ WKH J35206 ´3DUDPHWHU(VWLPDWLRQµWRRO7KHH[SHULPHQWDOGDWDZHUHILWWHGE\WKHPD[LPXPOLNHOLKRRG PHWKRG,WVREMHFWLYHIXQFWLRQ Φ LVJLYHQE\ ( ) ( ) ( ) 2 exp mod 2 2 1 1 1 ln 2 min ln 2 2 j NM NE jk jk jk j k jk X X N θ π σ σ = = ½ ª º − ° ° « » Φ = + + ® ¾ « » ° ° ¬ ¼ ¯ ¿ ¦ ¦ ZKHUH θ LVWKHVHWRISDUDPHWHUVWREHHVWLPDWHG H[S MN ; DQG PRG MN ; DUHWKH WK N PHDVXUHG DQGSUHGLFWHGYDOXHVUHVSHFWLYHO\IRUWKHFRQYHUVLRQLQH[SHULPHQW M MN σ LVWKHYDULDQFH LQFRQYHUVLRQ 1 UHSUHVHQWVWKHWRWDOQXPEHURIPHDVXUHPHQWVGXULQJDOOH[SHULPHQWV 1( UHSUHVHQWV WKH QXPEHU RI H[SHULPHQWV SHUIRUPHG DQG M 10 UHSUHVHQWV WKH QXPEHU RI PHDVXUHPHQWV RI FRQYHUVLRQ YDOXHV PDGH LQ H[SHULPHQW M 7KH SDUDPHWHU HVWLPDWLRQ WROHUDQFHZDVVHWWR DQGDFRQVWDQWYDULDQFHPRGHOZDVDVVXPHG .LQHWLF3DUDPHWHUV(VWLPDWLRQ 7RGHWHUPLQHWKHXQNQRZQFRQVWDQWVRIHDFKPRGHODSDUDPHWULFVWXG\ZDVSHUIRUPHGLQ ZKLFK WKH HIIHFWV RI FKDQJHV LQ GHVLJQ YDULDEOHV VXFK DV WKH LQLWLDO UHDFWLRQ PHGLXP
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 FRPSRVLWLRQWHPSHUDWXUHFDWDO\VWORDGLQJDQGSDUWLFOHVL]HZHUHDVVHVVHGDFFRUGLQJWRWKH H[SHULPHQWVSUHVHQWHGLQ7DEOH ([SHULPHQWV DOORZHG D ILUVW HVWLPDWLRQ RI WKH DSSDUHQW UHDFWLRQ DFWLYDWLRQ HQHUJ\ WKURXJKWKHLQLWLDOUHDFWLRQUDWHPHWKRGDQGWKH$UUKHQLXVHTXDWLRQ$YDOXHRI NPRO − ⋅ ZDVREWDLQHGZKLFKZDVXVHGDVDQLQLWLDOHVWLPDWHIRUWKHDFWLYDWLRQHQHUJ\RIWKHHQVXLQJ SDUDPHWHUHVWLPDWLRQV:KHQDGVRUSWLRQSDUDPHWHUVZHUHLQFOXGHGLQWKHUHDFWLRQUDWHODZ E\ WKH /++: PRGHO WKH YDOXH GHWHUPLQHG E\ *UDFࡤD HW DO IRU WKH ZDWHU HQWKDOS\ RI DGVRUSWLRQ NPRO − − ⋅ ZDV XVHG DV WKH LQLWLDO HVWLPDWH IRU WKLV YDULDEOH 7DEOH VXPPDUL]HV WKH UHVXOWV REWDLQHG E\ WKH SDUDPHWHU HVWLPDWLRQ SURFHGXUH LPSOHPHQWHG IRU ERWK WKH 3+ DQG /++: UHDFWLRQ UDWH ODZV )RU HDFK WKH DEVHQFH RU SUHVHQFH RI LQWHUQDO PDVVWUDQVIHUUHVLVWDQFHVZDVDVVHVVHG 7DEOH(VWLPDWHGNLQHWLFSDUDPHWHUVIRUWKH3+DQG/++:PRGHOVDQGUHVSHFWLYH REMHFWLYHIXQFWLRQYDOXHV 3DUDPHWHU 3+ 3+Z0DVV 7UDQVI5HV /++: /++:Z0DVV 7UDQVI5HV ( ) D ( NPRO − ⋅ ( ) PLQ F FDW N PRO J − − ⋅ ⋅ [ [ [ [ ( ) V : + NPRO − ∆ ⋅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− ⋅DQG DZDWHUHQWKDOS\RIDGVRUSWLRQRIî NPRO − ⋅ 7KHYDOXHHVWLPDWHGIRUWKHUHDFWLRQDFWLYDWLRQHQHUJ\LQWKLVZRUNLVHTXLYDOHQWWRWKRVH IRXQGE\RWKHUDXWKRUVIRUVHYHUDODFHWDOL]DWLRQVLQYROYLQJJO\FHUROFDWDO\VHGE\LRQH[FKDQJH UHVLQV$VSUHYLRXVO\PHQWLRQHG$JLUUHHWDOVWXGLHGWKHNLQHWLFEHKDYLRXURIWKHUHDFWLRQRI JO\FHUROZLWKIRUPDOGHK\GH DQGDFHWDOGHK\GH XVLQJ$PEHUO\VWDVFDWDO\VW7KHYDOXHV UHSRUWHG IRU WKH UHDFWLRQ DFWLYDWLRQ HQHUJLHV ZHUH NPRO − ⋅ DQG NPRO − ⋅
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− ⋅ ZDV HVWLPDWHG IRU WKH UHDFWLRQ DFWLYDWLRQHQHUJ\)RUWKHUHDFWLRQRIEXW\UDOGHK\GHZLWKJO\FHUROFDWDO\VHGE\$PEHUO\VW UHSRUWHG E\ *XHPH] HW DO DQ DSSDUHQW UHDFWLRQ DFWLYDWLRQ HQHUJ\ RI NPRO − ⋅ ZDV SUHGLFWHGXVLQJD3+PRGHO 0RUHRYHUWKHUHVXOWVREWDLQHGIRUWKHV\QWKHVLVRI*($WKURXJKDQDFHWDOL]DWLRQUHDFWLRQ FDQEHFRPSDUHGZLWKWKHUHVXOWVREWDLQHGE\;L+RQJHW DO E\WKHWUDQVDFHWDOL]DWLRQRI '((ZLWKJO\FHURO$VOLJKWO\KLJKHUDFWLYDWLRQHQHUJ\RI NPRO − ⋅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Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ ϬϰǁƚйĂƚĂůLJƐƚ;džƉͿ ϬϰǁƚйĂƚĂůLJƐƚ;DŽĚĞůͿ ϬϮǁƚйĂƚĂůLJƐƚ;džƉͿ ϬϮǁƚйĂƚĂůLJƐƚ;DŽĚĞůͿ
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 )LJXUH (IIHFWRIWHPSHUDWXUHRQWKHUHDFWLRQUDWH 3 EDU = LQLWLDO DFHWDOGHK\GHJO\FHUROPRODUUDWLRXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP (IIHFWRIWKH,QLWLDO&RPSRVLWLRQRIWKH5HDFWLRQ0HGLXP 7KH FRQYHUVLRQ DV D IXQFWLRQ RI WLPH IRU DQ HTXLPRODU PL[WXUH RI JO\FHURO DQG DFHWDOGHK\GHZDVFRPSDUHGZLWKWKHFRQYHUVLRQIRUDPL[WXUHZLWKDQDFHWDOGHK\GHJO\FHURO PRODUUDWLRRIWRDQDO\VHWKHHIIHFWRIWKHLQLWLDOPRODUUDWLRRIWKHUHDFWDQWV)LJXUH Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϱϬ ϭϬϬ ϭϱϬ ϮϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ dсϯϱϴ<ϬϰǁƚйĂƚ;džƉͿ dсϯϱϴ<ϬϰǁƚйĂƚ;DŽĚĞůͿ dсϯϱϯ<ϬϰǁƚйĂƚ;džƉͿ dсϯϱϯ<ϬϰǁƚйĂƚ;DŽĚĞůͿ dсϯϯϯ<ϬϰǁƚйĂƚ;džƉͿ dсϯϯϯ<ϬϰǁƚйĂƚ;DŽĚĞůͿ dсϯϱϯ<ϬϮǁƚйĂƚ;džƉͿ dсϯϱϯ<ϬϮǁƚйĂƚ;DŽĚĞůͿ dсϯϯϯ<ϬϮǁƚйĂƚ;džƉͿ dсϯϯϯ<ϬϮǁƚйĂƚ;DŽĚĞůͿ dсϯϭϯ<ϬϮǁƚйĂƚ;džƉͿ dсϯϭϯ<ϬϮǁƚйĂƚ;DŽĚĞůͿ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH (IIHFWRIWKHLQLWLDOUHDFWDQWPRODUUDWLRRQWKHUHDFWLRQUDWH 7 . = 3 EDU = ZW RIXQVLHYHG$PEHUO\VWVWLUULQJVSHHGRI USP )URPWKH UHVXOWVVKRZQLQ)LJXUHLWFDQEHREVHUYHGWKDWWKHUHDFWLRQSURFHHGHG IDVWHU ZKHQ RQH RI WKH UHDFWDQWV ZDV XVHG LQ H[FHVV DV FRXOG EH SUHGLFWHG E\ WKH LPSOHPHQWHGPRGHO 7KHHIIHFWRIWKHSUHVHQFHRIWKHSURGXFWVLQWKHLQLWLDOUHDFWLRQPL[WXUHZDVDOVRWHVWHG )LJXUH Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ ϭϮϱĐĞƚ'ůLJZĂƚŝŽ;džƉͿ ϭϮϱĐĞƚ'ůLJZĂƚŝŽ;DŽĚĞůͿ ϭϬĐĞƚ'ůLJZĂƚŝŽ;džƉͿ ϭϬĐĞƚ'ůLJZĂƚŝŽ;DŽĚĞůͿ
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 )LJXUH (IIHFWRQWKHUHDFWLRQUDWHRIWKHSUHVHQFHRISURGXFWVLQWKHLQLWLDOPL[WXUH 3 EDU = LQLWLDODFHWDOGHK\GHJO\FHUROPRODUUDWLR ZW RIXQVLHYHG$PEHUO\VW VWLUULQJVSHHGRI USP $V H[SHFWHG WKH LQLWLDO UHDFWLRQ UDWH ZDV ORZHU ZKHQ *($ DQG ZDWHU ZHUH LQWURGXFHG LQWR WKH LQLWLDO PL[WXUH 7KHVH UHVXOWV DUH UHODWHG WR WKH FKDQJH LQ WKH ´GULYLQJ IRUFHµ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µ DQG P µ DVVKRZQLQ)LJXUH Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ dсϯϰϯ<dž;tͿсdž;'Ϳсϳй;džƉͿ dсϯϰϯ<dž;tͿсdž;'Ϳсϳй;DŽĚĞůͿ dсϯϮϯ<dž;tͿсdž;'Ϳсϭϱй;džƉͿ dсϯϮϯ<dž;tͿсdž;'Ϳсϭϱй;DŽĚĞůͿ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 'D6LOYD&;$9/&*RQDOYHVDQG&-$0RWD:DWHUWROHUDQW]HROLWHFDWDO\VW IRUWKHDFHWDOLVDWLRQRIJO\FHURO*UHHQ&KHPLVWU\S 6LOYD 3+5 9/& *RQo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t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oD16/63DLV90706LOYDDQG$(5RGULJXHV2[\JHQDWHGELRIXHOVIURP EXWDQRO IRU GLHVHO EOHQGV 6\QWKHVLV RI WKH DFHWDO GLEXWR[\HWKDQH FDWDO\]HG E\ DPEHUO\VW LRQH[FKDQJH UHVLQ ,QGXVWULDO DQG (QJLQHHULQJ &KHPLVWU\ 5HVHDUFK S 4XLQWD )HUUHLUD 50 &$ $OPHLGD&RVWD DQG $( 5RGULJXHV +HWHURJHQHRXV 0RGHOV RI 7XEXODU 5HDFWRUV 3DFNHG ZLWK ,RQ([FKDQJH 5HVLQV࣯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
7 +(502'<1$0,&$1' . ,1(7,& 6 78'<2) *($ 6 <17+(6,67+528*+$1 $ &(7$/,=$7,21 5 ($&7,21 )LJXHLUHGR -/ DQG )5 5LEHLUR &DWiOLVH KHWHURJpQHD QG HG )XQGDomR &DORXVWH*XOEHQNLDQ ;X =3 DQG .7 &KXDQJ (IIHFW RI LQWHUQDO GLIIXVLRQ RQ KHWHURJHQHRXV FDWDO\WLF HVWHULILFDWLRQ RI DFHWLF DFLG &KHPLFDO (QJLQHHULQJ 6FLHQFH S /HYHQVSLHO2&KHPLFDO5HDFWLRQ(QJLQHHULQJUG(GLWLRQ-RKQ:LOH\6RQV 3|SNHQ7/*|W]HDQG-*PHKOLQJ5HDFWLRQNLQHWLFVDQGFKHPLFDOHTXLOLEULXPRI KRPRJHQHRXVO\ DQG KHWHURJHQHRXVO\ FDWDO\]HG DFHWLF DFLG HVWHULILFDWLRQ ZLWK PHWKDQRO DQG PHWK\O DFHWDWH K\GURO\VLV ,QGXVWULDO DQG (QJLQHHULQJ &KHPLVWU\ 5HVHDUFKS
&KDSWHU 6HOHFWLRQRID6ROYHQWIRUDQ ,QWHJUDWHG5HDFWLYH²$GVRUSWLYH3URFHVV IRUWKH6\QWKHVLVRI*($ $'$37(' )520 )DULD 539 3HUHLUD &60 6LOYD 9070 /RXUHLUR -0 5RGULJXHV $( *O\FHURO YDORULVDWLRQ DV ELRIXHOV 6HOHFWLRQ RI D VXLWDEOH VROYHQW IRU DQ LQQRYDWLYHSURFHVVIRUWKHV\QWKHVLVRI*($&KHPLFDO(QJLQHHULQJ-RXUQDOS ,QWURGXFWLRQ 7KH UHVHDUFK XQGHUWDNHQ LQ WKH SUHYLRXV FKDSWHU KDV FRQWULEXWHG WR D GHHSHU XQGHUVWDQGLQJRIWKHSKHQRPHQDXQGHUO\LQJWKHDFHWDOL]DWLRQUHDFWLRQEHWZHHQJO\FHURODQG DFHWDOGHK\GHXVLQJ$PEHUO\VWLRQH[FKDQJHUHVLQDVDFLGFDWDO\VW7KHDGYDQWDJHVRIWKLV UHDFWLRQURXWHRYHUDOWHUQDWLYHURXWHVIRUWKHV\QWKHVLVRI*O\FHURO(WK\O$FHWDO*($KDYH DOUHDG\EHHQH[SRVHG7KHIRUPDWLRQRIZDWHUDVDVHFRQGDU\SURGXFWUHSUHVHQWVWKHPDMRU GUDZEDFNRIWKLVUHDFWLRQ$V*($LVLQWHQGHGWREHDSSOLHGDVDIXHODGGLWLYHZDWHUPXVW RQO\EHSUHVHQWLQUHVLGXDODPRXQWVLQWKHILQDOSURGXFW&RQVHTXHQWO\WKHDVVD\UHTXLUHGIRU *($PLJKWLPSO\VLJQLILFDQWVHSDUDWLRQFRVWV,QWKLVVFHQDULRWKHXVHRIDPXOWLIXQFWLRQDO UHDFWRU LQWHJUDWLQJ UHDFWLRQ DQG VHSDUDWLRQ SURFHVVHV LQ D VLQJOH XQLW FRXOG UHSUHVHQW DQ HIILFLHQWVROXWLRQ
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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²DGVRUSWLYHSURFHVVHVVXFKDVWKH60%5ZDVGHYHORSHGLQ WKLV&KDSWHU$OLVWFRPSULVLQJWKHPRVWFRPPRQVROYHQWVLQFKHPLFDOSURFHVVHVZDVFRPSLOHG DQG VHTXHQWLDOO\ UHGXFHG EDVHG RQ WKHRUHWLFDOSDUDPHWHUV UHODWHG ZLWK UHDFWLYH²DGVRUSWLYH SURFHVVHV UHTXLUHPHQWV 7KH VROYHQWV WKDW SUHVHQWHG WKH EHVW UHVXOWV RQ WKH WKHRUHWLFDO
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 VFUHHQLQJZKHUHWKHQVXEMHFWHGWRH[SHULPHQWDOWHVWVWRDVVHVVLWVPLVFLELOLW\DGVRUSWLRQDQG UHDFWLRQ SURSHUWLHV ZLWK WKH VSHFLHV SUHVHQW LQ WKH VWXGLHG V\QWKHVLV V\VWHP DOORZLQJ WKH VHOHFWLRQRIDVXLWDEOHVROYHQWIRUWKHSURGXFWLRQRI*($LQD60%5 )LQDOO\ D NLQHWLF PRGHO ZDV SURSRVHG IRU WKH GLUHFW DFHWDOL]DWLRQ RI JO\FHURO ZLWK DFHWDOGHK\GHLQWKHSUHVHQFHRIWKHVHOHFWHGVROYHQW$SDUDPHWULFVWXG\FRPSULVLQJDZLGH UDQJHRIRSHUDWLQJFRQGLWLRQVZDVSHUIRUPHGLQRUGHUWRGHWHUPLQHWKHNLQHWLFSDUDPHWHUVIRU WKLVUHDFWLRQ7KHUHVXOWVZHUHFRPSDUHGZLWKWKRVHREWDLQHGIRUWKHVROYHQWIUHHUHDFWLRQ UHSRUWHGLQWKHSUHYLRXVFKDSWHU ([SHULPHQWDO'HVFULSWLRQ &KHPLFDOVDQG&DWDO\VWV 7KHFKHPLFDOVXVHGLQWKHH[SHULPHQWDOWHVWVZHUHDFHWDOGHK\GH!JO\FHURO! DFHWRQLWULOH ! DQG QQGLPHWK\OIRUPDPLGH ! SXUFKDVHG IURP 6LJPD²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².|QLJVKRIHQ*HUPDQ\7KH VDPSOHVZHUH LQLWLDOO\VWLUUHG LQ D YRUWH[PL[HU DQG WKHQ DOORZHGWRVWDQG WR SURPRWHWKH SKDVHVHSDUDWLRQ
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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üFKL/DERUDWRU\(TXLSPHQW)ODZLO6ZLW]HUODQGPHFKDQLFDOO\VWLUUHGDQGHTXLSSHGZLWKD EORZRIIYDOYHSUHVVXUHDQGWHPSHUDWXUHVHQVRUV)LJXUH7KHUHDFWRUZDVRSHUDWHGLQ EDWFK PRGH DQG LWV WHPSHUDWXUH ZDV FRQWUROOHG WKURXJK D ZDWHU EDWK /$8'$ /DXGD² .|QLJVKRIHQ*HUPDQ\ 7KH NLQHWLF VWXG\ ZDV SHUIRUPHG HYDOXDWLQJ WKH HIIHFW RI SDUDPHWHUV VXFK DV VWLUULQJ VSHHGUSPDQGUSPWHPSHUDWXUH . . DQG . LQLWLDODFHWDOGHK\GHWR JO\FHURO PRODU UDWLR DQG VROYHQW PRODU IUDFWLRQ DQG DQG FDWDO\VWORDGLQJ ZW DQG ZW RIWKHWRWDOUHDFWLRQPHGLXPPDVVDFFRUGLQJWRWKH H[SHULPHQWVGHVFULEHGLQ7DEOH7KHSUHVVXUHZDVVHWWR EDU ZLWKKHOLXPIRUDOOWKH H[SHULPHQWV9DSRXU²OLTXLGHTXLOLEULXPFDOFXODWLRQVLQGLFDWHGWKDWDWWKLVSUHVVXUHHYHQDW
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 WKHKLJKHURSHUDWLQJWHPSHUDWXUHWKHPRODUDPRXQWRIWKHUHDFWLRQPHGLXPVSHFLHVLQWKH YDSRXU SKDVH ZRXOG QRW H[FHHG RI WKH WRWDO PRODU DPRXQW LQWURGXFHG LQ WKH UHDFWRU DQGWKHUHIRUHWKHYDSRXUSKDVHZRXOGEHPDLQO\FRQVWLWXWHGE\KHOLXP 7DEOH.LQHWLFH[SHULPHQWVRSHUDWLQJFRQGLWLRQV ([S 1R 6WLUULQJ VSHHGUSP 7HPSHUDWXUH . ,QLWLDOUHDFWDQWV PRODUUDWLR 6ROYHQWPRODU IUDFWLRQQQ &DWDO\VW ORDGLQJZW 6DPSOHVZHUHFROOHFWHGDWSUHGHILQHGWLPHLQWHUYDOVDQGDQDO\VHGE\JDVFKURPDWRJUDSK\ DVGHVFULEHGLQVHFWLRQ(DFKUHDFWLRQNLQHWLFH[SHULPHQWZDVSHUIRUPHGRQO\RQFHLQ RUGHUWRNHHSWKHWHVWVPDQDJHDEOHDQGGXHWRKLJKUHDFWDQWVFRQVXPSWLRQ $QDO\WLFDO0HWKRGV 6DPSOHVFROOHFWHGLQWKHUHDFWLRQVROYHQWVFUHHQLQJSURFHGXUHGHILQHGLQVHFWLRQ ZHUHDQDO\VHGLQDJDVFKURPDWRJUDSK6KLPDG]X*&3OXVXVLQJDWKHUPDOFRQGXFWLYLW\ GHWHFWRU+HOLXP1 PLQ P/ − ⋅ ZDVXVHGDVWKHFDUULHUJDVIRUWKHVHSDUDWLRQRIWKH FRPSRXQGVLQ D&3:D[&% FROXPQZLWKDOHQJWKRI P PP RI LQWHUQDO GLDPHWHU DQG D ILOP WKLFNQHVV RI P µ 7KH SURSHU FROXPQ WHPSHUDWXUH SURJUDP ZDV GHILQHG IRU HDFKVROYHQW 7KH VDPH JDV FKURPDWRJUDSK\ HTXLSPHQW ZDV XVHG IRU WKH DQDO\VLV RI WKH VDPSOHV FROOHFWHGLQWKHGHWDLOHG NLQHWLFVWXG\RIWKHDFHWDOL]DWLRQUHDFWLRQLQWKHSUHVHQFHRIWKH VHOHFWHGVROYHQWGHVFULEHGLQVHFWLRQ7KHDQDO\VHVZHUHSHUIRUPHGE\LQMHFWLQJ / µ RIVDPSOHWRZKLFKDVSOLWUDWLRRIZDVDSSOLHG7KHWHPSHUDWXUHVRIWKHLQMHFWRU DQGWKHWKHUPDOFRQGXFWLYLW\GHWHFWRUZHUHVHWWR . 7KHFROXPQZDVLQLWLDOO\NHSWDW . IRU PLQ DQG LWV WHPSHUDWXUH ZDV WKHQ LQFUHDVHG DW D UDWH RI . PLQ − ⋅ XQWLO LW UHDFKHG . DQGKHOGFRQVWDQWDWWKDWYDOXHIRUWKHIROORZLQJ PLQ $IWHUWKLVSHULRGWKH
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²$ '62537,9( 3 52&(66)257+( 6 <17+(6,62) *($ FROXPQWHPSHUDWXUHZDVGHFUHDVHGWR . DWDUDWHRI . PLQ − ⋅ 7KHWRWDODQDO\VLVWLPH ZDV PLQ +HOLXP1DWDIORZUDWHRI PLQ P/ − ⋅ ZDVDOVRXVHGDVWKHFDUULHUJDV 6ROYHQW6HOHFWLRQ6WUDWHJ\IRU5HDFWLYH $GVRUSWLYH,QWHJUDWHG3URFHVVHV $V SUHYLRXVO\ VWDWHG QRQH RI WKH UHDFWDQWV RI WKH *($ V\QWKHVLV E\ PHDQV RI DQ DFHWDOL]DWLRQ UHDFWLRQ FDQ EH XVHG DV VROYHQW LQ WKH 60%5 WHFKQRORJ\ GXH WR SK\VLFDO RU FKHPLFDOFRQVWUDLQV7KHUHIRUHDWZRVWDJHPHWKRGRORJ\ZDVGHYHORSHGDQGDSSOLHGIRUWKH VHOHFWLRQRIWKHPRVWVXLWDEOHVROYHQWIRUWKHSURGXFWLRQRIWKLVDFHWDOE\UHDFWLYH²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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 7DEOH²3ULPDU\OLVWRIVROYHQWV 6ROYHQW &$61R 6ROYHQW &$61R 6ROYHQW &$61R 7ULFKORURWULIOXRURHWKDQH %XW\ODFHWDWH /DFWLFDFLG 7ULFKORUREHQ]HQH %XW\OFKORULGH 0HWKDQRO GLFKORUREHQ]HQH &KORUREHQ]HQH 0HWK\ODFHWDWH 'LPHWKR[\HWKDQH &KORURIRUP 0HWK\OHWK\ONHWRQH WULPHWK\OEHQ]HQH &LWULFDFLG 0HWK\OLVRDP\ONHWRQH GLFKORUREHQ]HQH &\FORKH[DQH 0HWK\OLVREXW\ONHWRQH GLR[RODQH &\FORKH[DQRO 0HWK\OQSURS\ONHWRQH GLR[DQH &\FORKH[DQRQH 0HWK\OWHUWEXW\OHWKHU EXWDQRO &\FORSHQWDQH 0HWK\OS\UUROLGRQH KHSWDQRO 'HFDQH QQGLPHWK\OIRUPDPLGH KH[DQRO 'LEURPRPHWKDQH QEXW\UDOGHK\GH KH[HQH 'LFKORURPHWKDQH 1RQDQH KH[\QH 'LHWK\OHWKHU 2FWDQH RFWDQRO 'LHWK\OHQHJO\FRO RGLFKORUREHQ]HQH SHQWDQRO 'LPHWK\ODFHWDPLGH 2[DOLFDFLG SURSDQRO 'LPHWK\OFDUERQDWH R[\OHQH DPLQRHWKDQRO 'LPHWK\OVXOIR[LGH 3HQWDQH EXWDQRO 'RGHFDQH 3URSLRQDOGHK\GH EXWDQRQH (WKDQRO 3URS\OHQHFDUERQDWH PHWK\OEXWDQH (WK\O$FHWDWH S[\OHQH SHQWDQRO (WK\OHQHFDUERQDWH 3\ULGLQH SHQWDQRQH (WK\OHQHGLFKORULGH WHUWEXW\ODOFRKRO SURSDQRO (WK\OHQHJO\FRO WHUWEXW\OPHWK\OHWKHU SHQWDQRO )RUPDOGHK\GH WHWUDFKORURPHWKDQH SHQWDQRQH )RUPLFDFLG 7HWUDK\GURIXUDQ $FHWLFDFLG *O\FHURO 7ROXHQH $FHWRQH +HSWDQH 7ULHWK\ODPLQH $FHWRQLWULOH +H[DQH 7ULIOXRURDFHWLFDFLG $FU\ORQLWULOH ,VREXWDQRO 9DOHUDOGHK\GH %HQ]HQH ,VREXW\UDOGHK\GH :DWHU %HQ]RQLWULOH ,VRRFWDQH %HQ]\ODOFRKRO ,VRSURS\ODFHWDWH 6ROYHQWVXVHGLQSUHYLRXVDFHWDOL]DWLRQUHDFWLRQVWXGLHV )RFXVLQJRQ3UHGLFWDEO\6XLWDEOH6ROYHQWV 7DNLQJ LQWR FRQVLGHUDWLRQ WKH GHYHORSPHQW RI D SURFHVV IRU WKH SURGXFWLRQ RI *($ E\ 60%5VROYHQWVWKDWKDYHEHHQUHSRUWHGDVUHDFWLYHZLWKDQ\RIWKHUHDFWDQWVRUSURGXFWVRI
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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±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·W+RIIODZVUHVSHFWLYHO\ZDVGHYHORSHG VLPLODUO\WRWKHPRGHOIRUWKHVROYHQWIUHHDFHWDOL]DWLRQUHDFWLRQSUHVHQWHGLQ6HFWLRQ (TXDWLRQVWR Ϭй ϭϬй ϮϬй ϯϬй ϰϬй ϱϬй ϲϬй ϳϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ ϳϬϬƌƉŵ ϱϬϬƌƉŵ
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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− ⋅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§ · − ¨ ¸ ¨ ¸ © ¹ ℜ = + + GEA W Ac Gly eq c s W W s D D C C C C K k K C K C ,QWKLVHTXDWLRQ ℜ UHSUHVHQWVWKHUHDFWLRQUDWHEDVHGRQORFDOLQWUDSDUWLFOHFRPSRVLWLRQ RI DFHWDOGHK\GH JO\FHURO *($ ZDWHU DQG '062 $FHW & *O\ & *($ & : & DQG ' & UHVSHFWLYHO\ V : . DQG V ' . UHSUHVHQWZDWHUDQG'062DGVRUSWLRQHTXLOLEULXPFRQVWDQWV7KH GHSHQGHQFHRI'062DGVRUSWLRQHTXLOLEULXPFRQVWDQWFDQDOVREHH[SUHVVHGE\WKH9DQ·W+RII ODZDVVKRZQLQHTXDWLRQ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 0 , , , exp s D s D s D H K K RT ∆ § · = − ¨ ¸ © ¹ 7KHYDULDEOH V ' . UHSUHVHQWWKH9DQ·W+RIIHTXDWLRQSUHH[SRQHQWLDOIDFWRUIRU'062 DQG V ' + ∆ UHSUHVHQWV'062DGVRUSWLRQHQWKDOS\ 7KH PRGHO HTXDWLRQV ZHUH VROYHG ZLWK J35206 *HQHUDO 3URFHVV 0RGHOOLQJ 6\VWHP YHUVLRQXVLQJRQHRILWVLQWHJUDWHGVROYHUV'$62/9GLVFUHWLVLQJWKHUDGLDOGLPHQVLRQLQ QRQXQLIRUPLQWHUYDOVDQGPDNLQJXVHRIDVHFRQGRUGHUFHQWUHGILQLWHGLIIHUHQFHPHWKRG 7KH GHWHUPLQDWLRQ RI WKH XQNQRZQ SDUDPHWHUV D ( F N : V +∆ V ' + ∆ : V . DQG V ' . ZDVFDUULHGRXWXVLQJWKH´3DUDPHWHU(VWLPDWLRQµWRRODQGILWWLQJWKHH[SHULPHQWDOGDWDE\ WKH PD[LPXPOLNHOLKRRG PHWKRG DVVXPLQJ D FRQVWDQW YDULDQFH PRGHO DQG VHWWLQJ WKH HVWLPDWLRQWROHUDQFHWR − )RUWKHGHWHUPLQDWLRQRIWKHHUURUVDVVRFLDWHGWRWKHSDUDPHWHUVHVWLPDWHGD-DFNNQLIH PHWKRGRORJ\ ZDVDSSOLHGFRQVLGHULQJJURXSVRIH[SHULPHQWVZKHUHRQHH[SHULPHQWZDV UHPRYHGIURPWKHRULJLQDOVHWRIH[SHULPHQWVH[SHULPHQWZDVQRWWDNHQLQWRDFFRXQWVLQFH QRH[WHUQDOPDVVWUDQVIHUOLPLWDWLRQVZHUHREVHUYHGDQGWKHUHIRUHWKHUHVXOWVDUHVLPLODUWR WKRVH REWDLQHG LQ H[SHULPHQW DQG LW ZDV FRQVLGHUHG WKDW WKH VDPH ´ZHLJKWµ VKRXOG EH JLYHQ WR HYHU\ H[SHULPHQW UHSUHVHQWLQJ D XQLTXH VHW RI RSHUDWLQJ FRQGLWLRQV RQ WKH SDUDPHWHUHVWLPDWLRQSURFHGXUH .LQHWLF3DUDPHWHUV(VWLPDWLRQ ,Q RUGHU WR PDNH D PRUH REMHFWLYH DVVHVVPHQW RI WKH TXDOLW\ RI WKH ILWWLQJ RI WKH H[SHULPHQWV FRQVLGHULQJ WKH SDUDPHWHUV HVWLPDWHG IRU WKH PDWKHPDWLFDO PRGHO LPSOHPHQWHGLWVFRUUHODWLRQFRHIILFLHQW &RUUHO 5 ZDVFRPSXWHGDFFRUGLQJWRHTXDWLRQ ( ) () 2 exp mod , , 1 1 2 2 exp exp , 1 1 1 = = = = − = − − ¦¦ ¦¦ NE NP i j i j i j Correl NE NP i j i j X X R X X ZKHUH H[S MN ; DQG PRG MN ; DUHWKH WK N PHDVXUHGDQGSUHGLFWHGYDOXHVUHVSHFWLYHO\IRUWKH FRQYHUVLRQLQH[SHULPHQW M H[S ; LVWKHDYHUDJHWKHH[SHULPHQWDOFRQYHUVLRQYDOXHV 1( LV
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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− ⋅ ( ) F FDW N GP PRO J V − − − ⋅ ⋅ ⋅ [ [ ( ) V : + NPRO − ∆ ⋅ ( ) V ' + NPRO − ∆ ⋅ ( ) V : . GP PRO − ⋅ [ [ ( ) V ' . GP PRO − ⋅ [ [ $VLWFDQEHREVHUYHGIURPWKHYDOXHVSUHVHQWHGLQ7DEOHWKHHVWLPDWLRQRIWKHVL[ SDUDPHWHUVIRUWKHSUHYLRXVO\GHVFULEHGPRGHOOHGWRODUJHVWDQGDUGHUURUV)RULQVWDQFHWKH VWDQGDUGHUURUVIRUWKHSUHH[SRQHQWLDOIDFWRUVIURPWKH$UUKHQLXVDQGWKH9DQ·W+RIIODZV DFKLHYHGDSSUR[LPDWHO\RILWVDEVROXWHYDOXHV)XUWKHUPRUHFRQWUDU\WRWKHH[SHFWHG WKH HVWLPDWLRQ SURFHGXUH VXJJHVWHG WKDW '062 FRXOG KDYH D KLJKHU DGVRUSWLRQ HTXLOLEULXP FRQVWDQW WKDQ ZDWHU UHJDUGOHVV WKH SDUDPHWHUV HVWLPDWLRQ HUURUV ZKLFK LV QRW WUXH IRU $PEHUO\VW DV LQGLFDWHG E\ WKH VZHOOLQJ WHVWV SUHVHQWHG LQ 6HFWLRQ 7KXV WKH VROXWLRQIRXQGWRHQKDQFHWKHNLQHWLFSDUDPHWHUVHVWLPDWLRQSUHFLVLRQDQGDWWHPSWWRDYRLG WKH LQFRQVLVWHQFLHV SUHVHQWHG FRPSULVHG WKH UHGXFWLRQ RI WKH QXPEHU RI SDUDPHWHUV WR EH GHWHUPLQHG 6LQFHWKHUDQJHRIRSHUDWLQJWHPSHUDWXUHVFDQEHFRQVLGHUHGQDUURZ . WKHHIIHFWRI WHPSHUDWXUHRQWKHDGVRUSWLRQHTXLOLEULXPZDVFRQVLGHUHGQHJOLJLEOHDQGHTXDWLRQVDQG ZHUHUHPRYHGIURPWKHILQDOPRGHO7KLVDVVXPSWLRQZDVEDVHGRQWKHUHVXOWVSXEOLVKHG IRURWKHUDFHWDOL]DWLRQUHDFWLRQVEHWZHHQDFHWDOGHK\GHDQGVHYHUDODOFRKROVGHVFULEHGE\D /++: UDWH ODZ LQ ZKLFK LW LV SRVVLEOH WR REVHUYH D PRUH VLJQLILFDQW WHPSHUDWXUH GHSHQGHQFHRIWKHNLQHWLFFRQVWDQWZKHQFRPSDUHGWRWKHDGVRUSWLRQFRQVWDQW)RULQVWDQFH IRUWKHDFHWDOL]DWLRQOHDGLQJWRWKHV\QWKHVLVRI'%( FRQVLGHULQJDWHPSHUDWXUHUDQJHIURP . WR . WKHZDWHUDGVRUSWLRQFRQVWDQWLVH[SHFWHGWRGHFUHDVHWRDSSUR[LPDWHO\RQH
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 WKLUGRILWVYDOXHZKLOHWKHLQFUHDVHRIWKHUHDFWLRQNLQHWLFFRQVWDQWUHDFKHVWHQWLPHVLWV YDOXHIURPWKHORZHUWRWKHKLJKHUWHPSHUDWXUH+HQFHWKHQHZYDOXHVHVWLPDWHGIRUWKH VLPSOLILHGPRGHOSDUDPHWHUV D ( F N : V . DQG V ' . DUHSUHVHQWHGLQ7DEOH 7DEOH²&RUUHFWHGHVWLPDWLRQRIWKHNLQHWLFSDUDPHWHUVIRUWKHDFHWDOL]DWLRQRIJO\FHUROLQ SUHVHQFHRI'062 3DUDPHWHUXQLWV (VWLPDWHG9DOXH 6WDQGDUG(UURU ( ) D ( NPRO − ⋅ ( ) F FDW N GP PRO J V − − − ⋅ ⋅ ⋅ [ [ ( ) V : . GP PRO − ⋅ [ [ ( ) V ' . GP PRO − ⋅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− ⋅ZDVHVWLPDWHG7KLVGHYLDWLRQPLJKW UHOD\ LQ VHYHUDO IDFWRUV )LUVWRI DOOWKH IRUPHU PRGHO LQ WKH DEVHQFH RI WKHVROYHQW KDV EHHQGHVFULEHGLQWHUPVRIDFWLYLWLHVZKLOHWKHPRGHOIRUWKLVQHZV\VWHPGRHVQRWDFFRXQW IRUWKHQRQLGHDOLW\RIWKHOLTXLGSKDVHGXHWRODFNRISDUDPHWHUVIRUWKHFRPSXWDWLRQRIWKH DFWLYLW\FRHIILFLHQWVDVSUHYLRXVO\GLVFXVVHG$GGLWLRQDOO\WKHLQIOXHQFHRIWKHWHPSHUDWXUH RQWKHDGVRUSWLRQHTXLOLEULXPZDVQRWFRQVLGHUHGIRUWKHUHDFWLRQLQWKHSUHVHQFHRI'062 VLQFHWKHQXPEHURISDUDPHWHUVWREHHVWLPDWHGZRXOGQRWDOORZDFRQVLVWHQWGHWHUPLQDWLRQ RIWKHLUYDOXHV$VDFRQVHTXHQFHWKHHVWLPDWHGDFWLYDWLRQHQHUJ\YDOXHPLJKWKDYHVXIIHUHG VRPH GHYLDWLRQV WR FRPSHQVDWH WKH HIIHFW RI WKH HQWKDOSLHV RI DGVRUSWLRQ LQ WKH UHDFWLRQ UDWH )LQDOO\ WKH KLJK SRODULW\ RI '062 DQG LWV FRUUHVSRQGLQJ DIILQLW\ WRZDUGV WKH UHVLQ PLJKW EH OHDGLQJ WR WKH KLQGHULQJ RI VRPH RI WKH DYDLODEOH DFWLYH VLWHV RI WKH FDWDO\VW GHFUHDVLQJWKHRYHUDOOUHDFWLRQUDWH7KHGLUHFWFRPSDULVRQEHWZHHQWKHDGVRUSWLRQFRQVWDQW YDOXHVKHUHUHSRUWHGDQGWKRVHIRUWKHVROYHQWIUHHV\VWHPLVQRWDOORZHG7KHWZRPRGHOV KDYHGLIIHUHQWFRQVLGHUDWLRQVRYHUWKHQRQLGHDOLW\RIWKHPL[WXUHDQGWKHYDOXHVHVWLPDWHG IRU WKHVH FRQVWDQWV DUH DIIHFWHG E\ WKHP +RZHYHU LW LV LPSRUWDQW WR PHQWLRQ WKDW DV
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²$ '62537,9( 3 52&(66)257+( 6 <17+(6,62) *($ H[SHFWHG GXH WR WKH ZHOONQRZQ KLJK DIILQLW\ RI ZDWHU WRZDUGV LRQ H[FKDQJH UHVLQV DV $PEHUO\VW D KLJKHU DGVRUSWLRQ FDSDFLW\ ZDV HVWLPDWHG IRU ZDWHU WKDQ IRU '062 1HYHUWKHOHVV LW LV LPSRUWDQW WR XQGHUOLQH WKDW QR GLUHFW PHDVXUHPHQW RI WKH DGVRUSWLRQ FRQVWDQWVZDVSHUIRUPHG,QVWHDGWKHYDOXHVSUHVHQWHGZHUHREWDLQHGWKURXJKWKHILWWLQJRI NLQHWLFGDWD,QDQ\FDVHLWLVLQWHQGHGWKDWWKRVHYDOXHVDUHFRKHUHQWEHWZHHQWKHPDQGLI QRWDFFXUDWHDWOHDVWWKH\VKRXOGKDYHVRPHSK\VLFDOPHDQLQJ ,Q WKH VXEVHTXHQW VHFWLRQ D PRUH GHWDLOHG DQDO\VLV RI WKH H[SHULPHQWDO DQG SUHGLFWHG NLQHWLFEHKDYLRXUZLOOEHDGGUHVVHG (IIHFWRI7HPSHUDWXUH $VGHVFULEHE\WKH$UUKHQLXVODZWKHUHDFWLRQUDWHVKRXOGEHIDYRXUHGE\WKHLQFUHDVHRI WHPSHUDWXUH7KDWWUHQGLVREVHUYHGLQWKHH[SHULPHQWDOUHVXOWVSUHVHQWHGLQ)LJXUH )LJXUH (IIHFWRIWHPSHUDWXUHRQWKHUHDFWLRQUDWH 3 EDU = LQLWLDO DFHWDOGHK\GHJO\FHUROPRODUUDWLRVROYHQWPRODUIUDFWLRQRIVWLUULQJVSHHGRI USP )LJXUHDOVRVKRZVWKDWWKHPRGHOLVDEOHWRGHVFULEHDFFXUDWHO\WKHHIIHFWRIFKDQJHV LQ WKH UHDFWLRQ WHPSHUDWXUH ZLWKLQ D UDQJH IURP . WR . LQGHSHQGHQWO\ IURP WKH FDWDO\VWORDGLQJ Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ dсϯϰϯ<ϬϯϬǁƚйĂƚ;džƉͿ dсϯϰϯ<ϬϯϬǁƚйĂƚ;DŽĚĞůͿ dсϯϮϯ<ϬϯϬǁƚйĂƚ;džƉͿ dсϯϮϯ<ϬϯϬǁƚйĂƚ;DŽĚĞůͿ dсϯϮϯ<ϬϭϱǁƚйĂƚ;džƉͿ dсϯϮϯ<ϬϭϱǁƚйĂƚ;DŽĚĞůͿ dсϯϬϯ<ϬϭϱǁƚйĂƚ;džƉͿ dсϯϬϯ<ϬϭϱǁƚйĂƚ;DŽĚĞůͿ
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Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ ƌĂƚŝŽсϮϬϭϬϯϬǁƚйĂƚ;džƉͿ ƌĂƚŝŽсϮϬϭϬϯϬǁƚйĂƚ;DŽĚĞůͿ ƌĂƚŝŽсϭϬϬϬϯϬǁƚйĂƚ;džƉͿ ƌĂƚŝŽсϭϬϬϬϯϬǁƚйĂƚ;DŽĚĞůͿ ƌĂƚŝŽсϬϱϬϬϭϱǁƚйĂƚ;džƉͿ ƌĂƚŝŽсϬϱϬϬϭϱǁƚйĂƚ;DŽĚĞůͿ ƌĂƚŝŽсϭϬϬϬϭϱǁƚйĂƚ;džƉͿ ƌĂƚŝŽсϭϬϬϬϭϱǁƚйĂƚ;DŽĚĞůͿ
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²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Ϭй ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ŽŶǀĞƌƐŝŽŶ dŝŵĞ;ŵŝŶͿ džƐŽůǀсϱϬйϬϯϬǁƚйĂƚ;džƉͿ džƐŽůǀсϱϬйϬϯϬǁƚйĂƚ;DŽĚĞůͿ džƐŽůǀсϳϱйϬϯϬǁƚйĂƚ;džƉͿ džƐŽůǀсϳϱйϬϯϬǁƚйĂƚ;DŽĚĞůͿ džƐŽůǀсϮϱйϬϭϱǁƚйĂƚ;džƉͿ džƐŽůǀсϮϱйϬϭϱǁƚйĂƚ;DŽĚĞůͿ džƐŽůǀсϱϬйϬϭϱǁƚйĂƚ;džƉͿ džƐŽůǀсϱϬйϬϭϱǁƚйĂƚ;DŽĚĞůͿ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 NLQHWLFV PLJKW DOVR EH UHODWHG ZLWK WKH KLQGHULQJ RI WKH DYDLODEOH DFWLYH VLWHV E\ '062 ZKLFKGXHWRLWVKLJKSRODULW\SUHVHQWVDKLJKDIILQLW\WRZDUGV$PEHU\VW &RQFOXVLRQV $OWKRXJK VRPH VROYHQW VFUHHQLQJ PHWKRGRORJLHV KDYH EHHQ UHSRUWHG LQ WKH RSHQ OLWHUDWXUH QRQH ZDV VSHFLILFDOO\ RULHQWHG IRU LQWHJUDWHG UHDFWLYH²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− ⋅ZDV HVWLPDWHGIRUWKHUHDFWLRQDFWLYDWLRQHQHUJ\:KHQFRPSDUHGZLWKWKHVROYHQWIUHHUHDFWLRQ WKH DGGLWLRQ RI '062 WR WKH V\VWHP DSSHDUV WR KDYH VRPH LPSDFW RQ WKH UHDFWLRQ SHUIRUPDQFHDVFRQVHTXHQFHRIWKHGLOXWLRQIDFWRUDQGWKHUHGXFWLRQRIDYDLODEOHFDWDO\VW DFWLYHVLWHVLPSRVHGE\LWVSUHVHQFH 1RWDWLRQ $EEUHYLDWLRQV '%( GLEXWKR[\HWKDQH
6 (/(&7,212)$ 6 2/9(17)25$1 , 17(*5$7(' 5 ($&7,9( ²$ '62537,9( 3 52&(66)257+( 6 <17+(6,62) *($ '(( GLHWKR[\HWKDQH '0( GLPHWKR[\HWKDQH '0) QQGLPHWK\OIRUPDPLGH '062 'LPHWK\O6XOIR[LGH *($ *O\FHURO(WK\O$FHWDO J35206 *HQHUDO3URFHVV0RGHOOLQJ6\VWHP /++: /DQJPXLU+LQVKHOZRRG+RXJHQ:DWVRQ 157/ 1RQ5DQGRP7ZR/LTXLG 60%5 6LPXODWHG0RYLQJ%HG5HDFWRU 81,)$& 8QLYHUVDO)XQFWLRQDO$FWLYLW\&RHIILFLHQW 81,48$& 8QLYHUVDO4XDVL&KHPLFDO 6\PEROV L & 0RODUFRQFHQWUDWLRQRIFRPSRXQGLLQWKHLQWUDSDUWLFOHIOXLG PRO GP − ⋅ ' 'LSROHPRPHQW D ( 5HDFWLRQ$FWLYDWLRQ(QHUJ\ NPRO − ⋅ * ∆ 6WDQGDUGUHDFWLRQ*LEEVIUHHHQHUJ\ NPRO − ⋅ V ' + ∆ '062HQWKDOS\RIDGVRUSWLRQ NPRO − ⋅ V : +∆ :DWHUHQWKDOS\RIDGVRUSWLRQ NPRO − ⋅ HT . 5HDFWLRQ(TXLOLEULXPFRQVWDQW F N 5HDFWLRQNLQHWLFFRQVWDQW FDW GP PRO J PLQ − − ⋅ ⋅ ⋅ F N $UUKHQLXVSUH H[SRQHQWLDOIDFWRUIRUWKHUHDFWLRQNLQHWLF FRQVWDQW FDW GP PRO J PLQ − − ⋅ ⋅ ⋅ V ' . '062DGVRUSWLRQHTXLOLEULXPFRQVWDQW GP PRO − ⋅ V ' . 9DQ·W+RIISUH H[SRQHQWLDOIDFWRUIRU'062DGVRUSWLRQ HTXLOLEULXPFRQVWDQW GP PRO − ⋅ V : . :DWHUDGVRUSWLRQHTXLOLEULXPFRQVWDQW GP PRO − ⋅ V : . 9DQ·W+RIISUH H[SRQHQWLDOIDFWRUIRUZDWHUDGVRUSWLRQ HTXLOLEULXPFRQVWDQW GP PRO − ⋅ /' 0HGLDQOHWKDOGRVH PJ NJ − ⋅ 1( 1XPEHURINLQHWLFH[SHULPHQWVSHUIRUPHG
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 ([SHULPHQWDO'HVFULSWLRQ &KHPLFDOV&DWDO\VWVDQG$GVRUEHQWV )RU WKH H[SHULPHQWV GHVFULEHG LQ WKLV &KDSWHU WKH IROORZLQJ FKHPLFDO FRPSRXQGV ZHUH DSSOLHG EOXH GH[WUDQ DFHWDOGHK\GH ! DQG JO\FHURO ! SXUFKDVHG IURP 6LJPD² $OGULFKGLPHWK\OVXOIR[LGH!IURP3URODERDQGZDWHUSXULILHGLQRXUODERUDWRULHV 7KH FKURPDWRJUDSKLF FROXPQ XVHG ZDV SDFNHG ZLWK $PEHUO\VW ZHW IURP 5RKP +DDV 7KLV PDFURUHWLFXODU LRQ H[FKDQJH UHVLQ FRPSRVHG E\ D VW\UHQH GLYLQ\OEHQ]HQH SRO\PHULFPDWUL[IXQFWLRQDOL]HGZLWKVXOIRQLFJURXSV 62 + DFWVVLPXOWDQHRXVO\DVFDWDO\VW DQGDGVRUEHQWIRUWKHVWXGLHGV\VWHP7DEOHVXPPDUL]HVWKHPDLQSK\VLFDOSURSHUWLHVRI $PEHUO\VWZHWSURYLGHGE\WKHVXSSOLHUDQGUHSRUWHGLQWKHRSHQOLWHUDWXUH 7DEOH²$PEHUO\VWZHWSK\VLFDOSURSHUWLHV 3URSHUW\ 9DOXH $FLG6LWHV&RQFHQWUDWLRQ HT+ NJ + 6XUIDFHDUHD P J $YHUDJHSRUHGLDPHWHU QP $YHUDJHSDUWLFOHGLDPHWHU P µ 3RURVLW\ ([SHULPHQWDO6HWXSDQG3URFHGXUH &KURPDWRJUDSKLF&ROXPQ&KDUDFWHUL]DWLRQ 7UDFHUH[SHULPHQWVZHUHFDUULHGRXWLQRUGHUWRDVVHVVWKHK\GURG\QDPLFVRIWKHIL[HG EHGXVHGIRUWKHGHWHUPLQDWLRQRIDGVRUSWLRQGDWDDQGIRUWKHV\QWKHVLVRI*($DGGUHVVHGLQ WKH SUHVHQW &KDSWHU 7KHVH H[SHULPHQWV FRQVLVWHG LQ WKH LQMHFWLRQ RI / µ SXOVHV RI D VROXWLRQRIEOXHGH[WUDQLQ'062DSSUR[LPDWHO\ J / − ⋅ LQWKHIL[HGEHGDQGUHFRUGLQJWKH RXWOHWFRQFHQWUDWLRQSURILOHXVLQJD899,6GHWHFWRU*LOVRQ0RGHO DW QP )LJXUH SUHVHQWV D VFKHPH RI WKH H[SHULPHQWDO VHWXS XVHG ZKLFK FRPSULVHV D +LJK 3UHVVXUH /LTXLG &KURPDWRJUDSK\ +3/& SXPS *LOVRQ 0RGHO D MDFNHWHG JODVV FROXPQ SDFNHG ZLWK $PEHUO\VW ZHW GHVFULEHG LQ 7DEOH D WKHUPRVWDWLF EDWK /$8'$ /DXGD²
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 .|QLJVKRIHQ *HUPDQ\ DQG D GHWHFWRU SRVLWLRQHG DW WKH RXWOHW RI WKH DIRUHPHQWLRQHG FROXPQ )LJXUH ² 6FKHPHRIWKH VHW XS XVHGIRUWUDFHUDQGEUHDNWKURXJKH[SHULPHQWV 7DEOH²)L[HGEHGFROXPQSURSHUWLHV 3URSHUW\ 9DOXH &DWDO\VW$GVRUEHQWZHLJKW J &ROXPQOHQJWK FP &ROXPQGLDPHWHU FP %XONGHQVLW\ − ⋅J FP 7KH H[SHULPHQWV ZHUH SHUIRUPHG XQGHU LVRWKHUPDO FRQGLWLRQV . DQG IORZ UDWHV UDQJLQJIURP PLQP/ − ⋅ WR PLQP/ − ⋅
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²%LQDU\EUHDNWKURXJKH[SHULPHQWDOFRQGLWLRQV %LQDU\ 0L[WXUH ( (( ( ) )) ) 4 P/ PLQ − −− − ⋅ ⋅⋅ ⋅ &RPSRXQG &RPSRXQG ( (( ( ) )) ) & PRO GP − −− − ⋅ ⋅⋅ ⋅ ( (( ( ) )) ) )HHG & PRO GP − −− − ⋅ ⋅⋅ ⋅ ( (( ( ) )) ) & PRO GP − −− − ⋅ ⋅⋅ ⋅ ( (( ( ) )) ) )HHG & PRO GP − −− − ⋅ ⋅⋅ ⋅ *O\FHURO '062 :DWHU '062 *($ '062
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 7KH VHWXS XVHG LQ WKHVH H[SHULPHQWV ZDV VLPLODU WR WKH SUHVHQWHG LQ )LJXUH +RZHYHU LQVWHDG RI XVLQJ DQ RQOLQH 899,6 GHWHFWRU VDPSOHV ZHUH FROOHFWHG SHULRGLFDOO\ DQG DQDO\VHG LQ D JDV FKURPDWRJUDSK *& 3OXV 6KLPDG]X -DSDQ HTXLSSHG ZLWK D WKHUPDOFRQGXFWLYLW\GHWHFWRUDQGD&3:D[&%FROXPQ$JLOHQW7HFKQRORJLHV8QLWHG6WDWHV RI$PHULFDWKURXJKWKHDQDO\WLFDOPHWKRGGHVFULEHGLQ6HFWLRQ *($6\QWKHVLVLQD)L[HG%HG$GVRUSWLYH5HDFWRU 7KH VWXG\ RI WKH SURGXFWLRQ RI *($ E\ D VRUSWLRQ HQKDQFHG UHDFWLYH SURFHVV ZDV SHUIRUPHGE\IHHGLQJWHUQDU\UHDFWLYHPL[WXUHVFRQWDLQLQJERWKDFHWDOL]DWLRQUHDFWDQWVDQG '062RUERWKSURGXFWVDQG'062WRDIL[HGEHGUHDFWRURSHUDWLQJLVRWKHUPDOO\DW . DQG PRQLWRULQJ WKH RXWOHW FRQFHQWUDWLRQ KLVWRULHV WKURXJKRXW WKH H[SHULPHQWV 7KH IHHG FRPSRVLWLRQDQGIORZUDWHVDUHVXPPDUL]HGLQ7DEOH 7KH VHWXS DQG DQDO\WLFDO PHWKRG XVHG LQ WKHVH H[SHULPHQWV ZHUH WKH VDPH DV WKH UHSRUWHGLQ6HFWLRQVDQG 7DEOH²7HUQDU\EUHDNWKURXJKH[SHULPHQWDOFRQGLWLRQV 7HUQDU\ 0L[WXUH 4 ( (( ( ) )) ) P/ PLQ − −− − ⋅ ⋅⋅ ⋅ &RPSRXQG &RPSRXQG &RPSRXQG & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ )HHG & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ )HHG & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ )HHG & ( (( ( ) )) ) PRO GP − −− − ⋅ ⋅⋅ ⋅ $FHWDOGHK\GH *O\FHURO '062 :DWHU *($ '062 7KH)L[HG%HG$GVRUSWLYH5HDFWRU 7KH H[SHULPHQWDO DQG PRGHO UHVXOWV REWDLQHG WKURXJKRXW WKH VWXG\ RI WKH DGVRUSWLRQ HTXLOLEULXPDQGWKHG\QDPLFIL[HGEHGRSHUDWLRQDUHUHSRUWHGZLWKLQWKLV6HFWLRQ
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² 6FKHPHRIWKHIL[HGEHGFROXPQ D DQGWKHPDVVWUDQVIHUPHFKDQLVPEHWZHHQ WKHEXONIOXLGDQGWKHFDWDO\VWDGVRUEHQWSDUWLFOHVE &RQVHTXHQWO\ VHSDUDWH EXON DQG SDUWLFOH PDVV EDODQFH HTXDWLRQV PXVW EH ZULWWHQ DV VKRZQLQHTXDWLRQVWR
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 ( ) ( ) 2 , , , , , , 2 16 ε ε ∂ ∂ ∂ − + + − = ∂ ∂ ∂ b i b i b i b LDF i b i p i ax b p uC C C k C C D t z d z ( ) , , 1= + − PT i p p i p i C C q ε ε ( ) ( ) , , , , , 6 1 ∂ = − + ℜ ∂ − PT i b LDF i b i p i i p i p b Ck C C C t d ρ νε ZKHUH E L & DQG 37 L & UHSUHVHQWWKHEXONDQGSDUWLFOHFRQFHQWUDWLRQVRIFRPSRXQG L ZLWK WKH ODWWHU EHLQJ UHODWHG WR WKH DYHUDJH SRUH DQG DGVRUEHG FRQFHQWUDWLRQV S L & DQG L T UHVSHFWLYHO\ W LVWLPH ] LVWKHD[LDOFRRUGLQDWH X LVWKHLQWHUVWLWLDOIOXLGYHORFLW\ D[ ' LV WKHD[LDOGLVSHUVLRQFRHIILFLHQW /') L N LVWKHJOREDOPDVVWUDQVIHUFRHIILFLHQWRIFRPSRXQG L E ε DQG S ε DUH WKH EHG DQG SDUWLFOH SRURVLW\ E ρ LV WKH EXON GHQVLW\ S G LV WKH SDUWLFOH GLDPHWHU L ν LV WKH VWRLFKLRPHWULF FRHIILFLHQW RI FRPSRXQG L DQG ℜ LV WKH UHDFWLRQ UDWH GHVFULEHG LQ WHUPV RI FRQFHQWUDWLRQV E\ WKH /DQJPXLU+LQVKHOZRRG+RXJHQ:DWVRQ /++: ODZHTXDWLRQDFFRUGLQJWRWKHNLQHWLFVWXG\SUHVHQWHGLQ6HFWLRQ )RU WKH UHVROXWLRQ RI WKLV V\VWHP RI SDUWLDO GLIIHUHQWLDO HTXDWLRQV DQ LQLWLDO FRQGLWLRQ FRUUHVSRQGLQJWRWKHVDWXUDWLRQRIWKHIL[HGEHGSULRUWRWKHH[SHULPHQWVDQGWZRERXQGDU\ FRQGLWLRQV IRUPXODWHG E\ 'DQFNZHUWV IRU WKH LQOHW DQG RXWOHW RI WXEXODU UHDFWRUV ZHUH GHILQHGDFFRUGLQJWRHTXDWLRQVWR 0 , , , 0,= ∀ → = = b i p i b i t z C C C , , , 0 0 0, = = ∂ = ∀ → = − ∂ b i in i b i ax z z C z t uC u C D z , , 0 b i z L C z L t z = ∂ = ∀ → = ∂ $VWKHEXONFRQFHQWUDWLRQLVFRQWLQXRXVO\FKDQJLQJWKURXJKRXWDFKURPDWRJUDSKLFSURFHVV WKHIOXLGLQWHUVWLWLDOYHORFLW\LVH[SHFWHGWRXQGHUJRVOLJKWIOXFWXDWLRQVGXHWRWKHGLIIHUHQW PRODUYROXPHV 0 L 9 RIWKHVSHFLHVLQYROYHG7KHVHYDULDWLRQVZHUHDFFRXQWHGIRUEDVHGRQ WKHWRWDOPDVVEDODQFHDQGDUHH[SUHVVHGE\HTXDWLRQDQGWKHFRUUHVSRQGLQJERXQGDU\ FRQGLWLRQHTXDWLRQ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 ( ) , , , , 1 16 = − ∂= − − ∂ ¦ NC b LDF i M i b i p i i b p uk V C C z d ε ε 0 0, = = ∀ → = z z t u u 7KH GHWHUPLQDWLRQ RI WKH JOREDO PDVV WUDQVIHU FRHIILFLHQW /') L N DV D IXQFWLRQ RI WKH LQWHUQDODQGH[WHUQDOPDVV WUDQVIHUFRHIILFLHQWV LQW L N DQG H[W L N UHVSHFWLYHO\ZDVFDUULHG RXWE\HVWDEOLVKLQJDQDQDORJ\WRWKHDVVRFLDWLRQRIUHVLVWRUVLQVHULHVLQHOHFWULFDOV\VWHPV HTXDWLRQDVFRPPRQO\UHSRUWHGLQWKHRSHQOLWHUDWXUH , t, int, 1 1 1 ε = + LDF i ex i p i k k k 1RGLUHFWPHDVXUHRIWKHPDVVWUDQVIHUFRHIILFLHQWVZDVSHUIRUPHGLQWKLVZRUN,QVWHDG WKHLUYDOXHVZHUHHVWLPDWHGEDVHGRQFRUUHODWLRQV7KHLQWHUQDOPDVVWUDQVIHUFRHIILFLHQWZDV FRPSXWHGDFFRUGLQJWRHTXDWLRQ , , 10 = eff i int i p D kd ZKHUH HII L ' LV WKH HIIHFWLYH GLIIXVLRQ FRHIILFLHQW RI FRPSRXQG L LQ D PXOWLFRPSRQHQW PL[WXUH GHWHUPLQHG E\ DSSO\LQJ WKH 3HUNLQV DQG *HDQNRSOLV PL[LQJ UXOH WR WKH LQILQLWH GLOXWLRQGLIIXVLRQFRHIILFLHQWVHVWLPDWHGE\WKH6FKHLEHO HTXDWLRQDQGDVVXPLQJDSDUWLFOH WRUWXRVLW\ YDOXH HTXDO WR WKH LQYHUVH RI WKH SDUWLFOH SRURVLW\ DV UHSRUWHG E\ :DNDR DQG 6PLWK VHH$SSHQGL[IRUPRUHGHWDLOV 7KH H[WHUQDO PDVV WUDQVIHU FRHIILFLHQW ZDV SUHGLFWHG E\ WKH :LOVRQ DQG *HDQNRSOLV FRUUHODWLRQ GHVFULEHGE\HTXDWLRQ ( ) 0.33 1.09 p p b Sh Re Sc ε = 7KH6KHUZRRG5H\QROGVHYDOXDWHGDWWKHSDUWLFOHFRQGLWLRQVDQG6FKPLGWGLPHQVLRQOHVV QXPEHUV S 6K S 5H DQG 6F DUHGHILQHGE\HTXDWLRQVDQGFRUUHVSRQGLQJO\
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 , , = ext i p p i m k d Sh D = ρ µ p p ud Re , i m Sc D µ ρ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max,i , , 1 = + ¦ i p i iNC j p i j Q K C q K C
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ax uL Pe D = 7KHFROXPQUHVSRQVHWRDQLQMHFWLRQRID NJ P − ⋅VROXWLRQRIEOXHGH[WUDQLQ'062DW GLIIHUHQWIORZUDWHVZDVPRQLWRUHGXVLQJD899,6GHWHFWRU'XHWRWKHGLOXWLRQLPSRVHGWR WKH WUDFHU VSHFLHV LW ZDV UHDVRQDEOH WR DVVXPH D SURSRUWLRQDO UHODWLRQ EHWZHHQ LWV FRQFHQWUDWLRQDQGWKHGHWHFWRUVLJQDO 7KHEOXHGH[WUDQKLJKPROHFXODUVL]HSUHFOXGHVLWVSHQHWUDWLRQLQ$PEHUO\VWSDUWLFOH SRUHV7KHUHIRUHWKHEHGSRURVLW\FRXOGEHFRPSXWHGWKURXJKWKHUDWLREHWZHHQWKHVSDFH WLPH τ DQGWKHPHDQUHVLGHQFHWLPH U W GHWHUPLQHGIURPWKHILUVWVWDWLVWLFDOPRPHQWRI WKH UHVLGHQFH WLPH GLVWULEXWLRQ FXUYHV HTXDWLRQ 7KH 3HFOHW QXPEHU RQ WKH RWKHU KDQGZDVHVWLPDWHGEDVHGRQWKHYDULDQFHRIWKHH[SHULPHQWDOUHVLGHQFHWLPHGLVWULEXWLRQ FXUYHVGHWHUPLQHGE\LWVVHFRQGVWDWLVWLFDOPRPHQWHTXDWLRQ7DEOHSUHVHQWVWKH IL[HG EHG FKDUDFWHULVWLFV H[SHULPHQWDOO\ GHWHUPLQHG E\ WKH WUDFHU H[SHULPHQWV E\ WKH PRPHQWVPHWKRG
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 ( ) ( ) ( ) 0 ∞ = ³ out out C t E t C t dt ( ) 0 r b FB tE t dt t V Q ετ ∞ = = ³ ( ) ( ) 2 2 22 0 2 2 r r tr t t Pe t t E t dt σ ∞ = = − ³ 7KHYDULDEOHV ( ) ( W )% 9 DQG 4 UHSUHVHQWWKHUHVLGHQFHWLPHGLVWULEXWLRQWKHIL[HGEHG UHDFWRUYROXPHDQGWKHIHHGIORZUDWHUHVSHFWLYHO\ 7DEOH7UDFHUH[SHULPHQWVUHVXOWV ( (( ( ) )) ) 4 P/ PLQ − −− − ⋅ ⋅⋅ ⋅ ( (( ( ) )) ) U W PLQ E ε εε ε W σ σσ σ 3H $VUHDFWLRQDGVRUSWLRQDQGPDVVWUDQVIHUPHFKDQLVPVEHWZHHQWKHEXONDQGWKHSDUWLFOH DUH DEVHQW LQ WUDFHU H[SHULPHQWV WKH IL[HG EHG PRGHO SUHVHQWHG LQ 6HFWLRQ FDQ EH UHGXFHGWRDVLPSOHGLVSHUVLYHIORZPDVVEDODQFHHTXDWLRQDQGWKHUHVSHFWLYHLQLWLDO DQGERXQGDU\FRQGLWLRQVHTXDWLRQVWR 2 , , , 2 ∂ ∂ ∂ + = ∂ ∂ ∂ b i b i b i ax C C C u D t z z )LJXUHVKRZVWKHH[SHULPHQWDODQGVLPXODWHGUHVLGHQFHWLPHGLVWULEXWLRQFXUYHV
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH ([SHULPHQWDODQGSUHGLFWHGEUHDNWKURXJKFXUYHVIRUWKHELQDU\ *($ '062DW . DQGIORZUDWHVRIDSSUR[LPDWHO\ P/ PLQ − ⋅ DDQG P/ PLQ − ⋅ E 7KH GLUHFW REVHUYDWLRQ RI WKH SUHYLRXV ILJXUHV LQGLFDWHV WKDW WKH PRGHO LV LQ JRRG DJUHHPHQW ZLWK WKH H[SHULPHQWV 1HYHUWKHOHVV WKH TXDOLW\ RI WKH SUHVHQWHG ILWWLQJV ZDV TXDQWLILHGE\FRPSXWLQJLWVFRUUHODWLRQFRHIILFLHQW &RUUHO 5 DFFRUGLQJWRHTXDWLRQ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ Ϯϱ ϱϬ ϳϱ ϭϬϬ Ϭ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϭϳϱ ϮϭϬ D^K ;ŵŽůͼ>ͲϭͿ ' ;ŵŽůͼ>ͲϭͿ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ĂͿ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ Ϯϱ ϱϬ ϳϱ ϭϬϬ Ϭ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ D^K ;ŵŽůͼ>ͲϭͿ ' ;ŵŽůͼ>ͲϭͿ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ďͿ
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 ( ) () 2 exp mod , , , , , , 1 1 1 2 2 mod exp , , , , 1 1 1 1 = = = = = = − = − − ¦¦¦ ¦¦¦ NC NE NP out i j k out i j k i j k Correl NC NE NP out i j k out i i j k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− ⋅ P/ PLQ 7KH WHPSHUDWXUHZDVNHSWDW . DQGWKHHTXLSPHQWZDVRSHUDWHGDWDWPRVSKHULFSUHVVXUH $IWHU UHDFKLQJ WKH VWHDG\ VWDWH DSSUR[LPDWHO\ PLQ DIWHU WKH EHJLQQLQJ RI WKH H[SHULPHQWWKHUHDFWLRQPHGLDZDVHOXWHGIURPWKHUHDFWRUE\IHHGLQJDSXUH'062VWUHDP DW − ⋅ P/ PLQ 7KH H[SHULPHQWDO UHVXOWV DUH SUHVHQWHG LQ )LJXUH WRJHWKHU ZLWK WKH VLPXODWLRQV REWDLQHG WKURXJK WKH PDWKHPDWLFDO PRGHO GHYHORSHG LQ 6HFWLRQ DQG WKH DGVRUSWLRQ DQG UHDFWLRQ GDWD SUHYLRXVO\ FROOHFWHG +RZHYHU RQH PXVW PHQWLRQ WKDW WKH DFHWDOGHK\GH DGVRUSWLRQ LVRWKHUP ZDV LPSRVVLEOH WR EH GHWHUPLQHG VLQFH WKLV FRPSRXQG XQGHUJRHVROLJRPHUL]DWLRQUHDFWLRQVZKHQLQFRQWDFWZLWKDFLGV ,QVWHDGWKHDGVRUSWLRQ SDUDPHWHUV IRU WKLV FRPSRXQG ZHUH DVVXPHG WR EH HTXDO WR WKRVH REWDLQHG IRU JO\FHURO EDVHGRQ WKHVLPLODULW\ RIWKH EUHDNWKURXJK FXUYHV RI WKHWZRFRPSRXQGVLQ WKH IL[HG EHG DGVRUSWLYHUHDFWRU
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH ² 6\QWKHVLVRI*($LQ DIL[HGEHGDGVRUSWLYHUHDFWRU DW . E\IHHGLQJ D VROXWLRQFRQWDLQLQJ − ⋅ PRO / RIDFHWDOGHK\GH − ⋅ PRO / RIJO\FHURODQG − ⋅ PRO / RI'062DW − ⋅ P/ PLQ DDQGUHJHQHUDWLRQRIWKHEHGZLWKSXUH'062DW − ⋅ P/ PLQ E ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϱϬ ϭϬϬ ϭϱϬ ϮϬϬ ϮϱϬ ϯϬϬ ;ŵŽůͼ>ͲϭͿ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ 'ůLJĐĞƌŽů;džƉͿ 'ůLJĐĞƌŽů;DŽĚĞůͿ ĐĞƚĂůĚĞŚLJĚĞ;džƉͿ ĐĞƚĂůĚĞŚLJĚĞ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ĂͿ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϱϬ ϭϬϬ ϭϱϬ ϮϬϬ ;ŵŽůͼ> Ͳϭ Ϳ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ 'ůLJĐĞƌŽů;džƉͿ 'ůLJĐĞƌŽů;DŽĚĞůͿ ĐĞƚĂůĚĞŚLJĚĞ;džƉͿ ĐĞƚĂůĚĞŚLJĚĞ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ďͿ
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 )LJXUHDVKRZVWKDWJO\FHURODQGDFHWDOGHK\GHZHUHWKHILUVWVSHFLHVWRHOXWHIURP WKH IL[HG EHG UHDFWRU DIWHU DSSUR[LPDWHO\ PLQ 7KH FRQWLQXHG FRQWDFW EHWZHHQ WKH UHDFWDQWVDQGWKHDFLGLRQH[FKDQJHUHVLQFDWDO\VWSURPRWHGWKHIRUPDWLRQRIZDWHUDQG*($ DFKLHYLQJ FRQFHQWUDWLRQV DERYH − ⋅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
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH²,QWHUQDOFRQFHQWUDWLRQSURILOHVRIWKHIL[HGEHGDGVRUSWLYHUHDFWRU PLQ D P LQ E PLQ F DQG PLQ GDIWHUWKHEHJLQQLQJRIWKHV\QWKHVLVRI*($E\IHHGLQJDVROXWLRQFRQWDLQLQJ − ⋅ PRO / RI DFHWDOGHK\GH − ⋅ PRO / RIJO\FHURODQG − ⋅ PRO / RI'062DW − ⋅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ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϬϮ Ϭϰ Ϭϲ Ϭϴ ϭϬ ;ŵŽůͼ>ͲϭͿ nj> ĂͿ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϬϮ Ϭϰ Ϭϲ Ϭϴ ϭϬ ;ŵŽůͼ>ͲϭͿ nj> ďͿ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϬϮ Ϭϰ Ϭϲ Ϭϴ ϭϬ ;ŵŽůͼ> Ͳϭ Ϳ nj> ĐͿ ϬϬ ϯϱ ϳϬ ϭϬϱ ϭϰϬ ϬϬ ϬϮ Ϭϰ Ϭϲ Ϭϴ ϭϬ ;ŵŽůͼ> Ͳϭ Ϳ nj> ĚͿ 'ůLJĐĞƌŽů ĐĞƚĂůĚĞŚLJĚĞ tĂƚĞƌ ' D^K
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ϮϬй ϰϬй ϲϬй ϴϬй ϭϬϬй ϭ ϭϬ ϭϬϬ ϭϬϬϬ ŽŶǀĞƌƐŝŽŶ ʏ ;ŵŝŶͿ ^ƚĞĂĚLJ^ƚĂƚĞŽŶǀĞƌƐŝŽŶ DĂdžŝŵƵŵŽŶǀĞƌƐŝŽŶ ƋƵŝůŝďƌŝƵŵŽŶǀĞƌƐŝŽŶ
* /<&(52/$&(7$/6352'8&7,21%< 6 ,08/$7(' 0 29,1* % (' 5 ($&725 )LJXUH ([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVR EWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WRDIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI '062DW . )LJXUH ([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WRDIL[HG EHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062 DW . ϭϭϬ ϭϭϲ ϭϮϮ ϭϮϴ ϭϯϰ ϭϰϬ ϬϬ Ϭϰ Ϭϴ ϭϮ ϭϲ ϮϬ ϬϬ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ D^K ;ŵŽůͼ> Ͳϭ Ϳ ;ŵŽůͼ> Ͳϭ Ϳ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ϭϭϬ ϭϭϲ ϭϮϮ ϭϮϴ ϭϯϰ ϭϰϬ ϬϬ Ϭϰ Ϭϴ ϭϮ ϭϲ ϮϬ ϬϬ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ D^K ;ŵŽůͼ> Ͳϭ Ϳ ;ŵŽůͼ> Ͳϭ Ϳ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 )LJXUH ([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WRDIL[HGEHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI '062DW . )LJXUH ([SHULPHQWDODQGVLPXODWHGEUHDNWKURXJKFXUYHVREWDLQHGE\IHHGLQJ − ⋅ PRO / RIZDWHUDQG − ⋅ PRO / RI'062DWDIORZUDWHRI − ⋅ P/ PLQ WRDIL[HG EHGVDWXUDWHGZLWK − ⋅ PRO / RIZDWHU − ⋅ PRO / RI*($DQG − ⋅ PRO / RI'062 DW . ϭϮϬ ϭϮϰ ϭϮϴ ϭϯϮ ϭϯϲ ϭϰϬ ϬϬ Ϭϰ Ϭϴ ϭϮ ϭϲ ϮϬ ϬϬ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ D^K ;ŵŽůͼ> Ͳϭ Ϳ ;ŵŽůͼ> Ͳϭ Ϳ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ ϭϮϬ ϭϮϰ ϭϮϴ ϭϯϮ ϭϯϲ ϭϰϬ ϬϬ Ϭϰ Ϭϴ ϭϮ ϭϲ ϮϬ ϬϬ ϭϬϬ ϮϬϬ ϯϬϬ ϰϬϬ ϱϬϬ ϲϬϬ D^K ;ŵŽůͼ> Ͳϭ Ϳ ;ŵŽůͼ> Ͳϭ Ϳ dŝŵĞ;ŵŝŶͿ ';džƉͿ ';DŽĚĞůͿ tĂƚĞƌ;džƉͿ tĂƚĞƌ;DŽĚĞůͿ D^K;džƉͿ D^K;DŽĚĞůͿ
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− ⋅ P/ PLQ DQG − ⋅ P/ PLQ 7KH3HFOHWQXPEHUZDVXVHGDVDPHDVXUHPHQWRIWKHUDWLR EHWZHHQ WKH FRQYHFWLYH DQG GLVSHUVLYH HIIHFWV IRU ZKLFK DQ DYHUDJH YDOXH RI ZDV HVWLPDWHG $GVRUSWLRQHTXLOLEULXPGDWDDW . ZHUHREWDLQHGE\SHUIRUPLQJVHYHUDOEUHDNWKURXJK H[SHULPHQWVZLWKQRQUHDFWLYHSDLUVRIFRPSRXQGVIROORZLQJDIURQWDODQDO\VLVPHWKRGRORJ\ 7KH H[SHULPHQWDO GDWD FROOHFWHG ZHUH ILWWHG E\ D /DQJPXLUFRPSHWLWLYHDGVRUSWLRQ PRGHO 7KHYDOXHVGHWHUPLQHGIRUJO\FHUROZDWHU*($DQG'062DGVRUSWLRQHTXLOLEULXPFRQVWDQWV ZHUH ± / PRO − ⋅ ± / PRO − ⋅ ± / PRO − ⋅ DQG ±
6 2537,21 ( 1+$1&(' 5 ($&7,9( 3 52&(66)257+( 6 <17+(6,62) *($ 7 +( ) ,;(' % (' $ '62537,9( 5 ($&725 / PRO − ⋅ UHVSHFWLYHO\ 7KHLU PRQROD\HU PD[LPXP FDSDFLWLHV ZHUH ± $GV PRO / − ⋅ ± $GV PRO / − ⋅ ± $GV PRO / − ⋅ DQG ± $GV PRO / − ⋅ E\WKHVDPHRUGHU +HQFHLWLVSRVVLEOHWRFRQILUPWKDW$PEHUO\VWKDVDKLJKVHOHFWLYLW\WRZDUGVZDWHU2Q WKH RWKHU KDQG *($ SUHVHQWHG WKH ORZHVW DGVRUSWLRQ 7KH GHWHUPLQDWLRQ RI DGVRUSWLRQ HTXLOLEULXP GDWD IRU DFHWDOGHK\GH ZDV QRW SRVVLEOH VLQFH WKLV DOGHK\GH UHDFWV IRUPLQJ ROLJRPHUV LQ WKH SUHVHQFH RI DFLGV +RZHYHU WKH H[SHULPHQWDO UHVXOWV LQGLFDWHG WKDW WKH DGVRUSWLRQSDUDPHWHUVHVWLPDWHGIRUJO\FHUROUHSUHVHQWDJRRGHVWLPDWHIRUWKHGHVFULSWLRQRI DFHWDOGHK\GHDGVRUSWLRQHTXLOLEULXP *($ ZDV V\QWKHVLVHG E\ IHHGLQJ − ⋅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