A Direct Observation of the Fine Aromatic Clusters and Molecular

Subscriber access provided by University of Newcastle, Australia

Article

A direct observation of the fine aromatic clusters and molecular structures of biochars Xin Xiao, and Baoliang Chen Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b06300 • Publication Date (Web): 12 Apr 2017 Downloaded from http://pubs.acs.org on April 12, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Environmental Science & Technology is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 27

Environmental Science & Technology

$ GLUHFW REVHUYDWLRQ RI WKH ILQH DURPDWLF FOXVWHUV DQG PROHFXODU VWUXFWXUHV RI ELRFKDUV

;LQ ;LDR

%DROLDQJ &KHQ

'HSDUWPHQW RI (QYLURQPHQWDO 6FLHQFH =KHMLDQJ 8QLYHUVLW\ +DQJ]KRX

&KLQD

=KHMLDQJ 3URYLQFLDO .H\ /DERUDWRU\ RI 2UJDQLF 3ROOXWLRQ 3URFHVV DQG &RQWURO +DQJ]KRX

&RUUHVSRQGLQJ $XWKRU 3KRQH

)D[

(PDLO EOFKHQ#]MX HGX FQ

0DQXVFULSW FRQWDLQV 7H[W

ZRUGV )LJXUHV

ZRUGV

ACS Paragon Plus Environment

&KLQD


Page 2 of 27

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

QP DQG GHFRUDWH WKH

JUDSKHQH OLNH DJJUHJDWHV DW GLIIHUHQW GHSWKV 7KH 6WRQH :DOHV WUDQVIRUPDWLRQ LQ WKH GLVSHUVHG ELRFKDUV ZDV REVHUYHG ZKLFK LV FULWLFDO WR IRUP FDUERQ QDQRWXEHV IXOOHUHQHV DQG RWKHU FDUERQ QDQRVWUXFWXUHV LQ WKH QDWXUDO HQYLURQPHQW ,Q DGGLWLRQ WKH & & ERQG OHQJWK GHFUHDVHV DV WKH S\URO\VLV WHPSHUDWXUH LQFUHDVHV IURP

ƒ& WR

ƒ& LQGLFDWLQJ WKDW DOLSKDWLF FDUERQ WUDQVIRUPV LQWR DURPDWLF FDUERQ 7KH

TXDWHUQDU\ VWUXFWXUH RI ELRFKDU LQFOXGLQJ KHWHURJHQHRXV SKDVHV JUDSKHQH OLNH DJJUHJDWHV QDQRVL]HG DURPDWLF FOXVWHUV DQG DWRPLF DUUDQJHPHQWV LV FRQFHSWXDOL]HG WR HQKDQFH RXU NQRZOHGJH RI WKH ELRFKDU VWUXFWXUH ZKLFK JUHDWO\ DLGV LQ XQGHUVWDQGLQJ WKH QRYHO IXQFWLRQV RI ELRFKDU DQG RIIHUV D PROHFXODU JXLGH IRU SRWHQWLDO DSSOLFDWLRQV RI ELRFKDU


Page 3 of 27




Page 4 of 27

,QWURGXFWLRQ %LRFKDU LV D FDUERQ ULFK SURGXFW WKDW LV S\URO\]HG IURP ELRPDVV DQG RWKHU ZDVWHV XQGHU R[\JHQ OLPLWHG FRQGLWLRQV DQG LW LV JDLQLQJ LQFUHDVHG DWWHQWLRQ LQ HQHUJ\ XWLOL]DWLRQ FOLPDWH FKDQJH PLWLJDWLRQ LPSURYHG VRLO FDUERQ VHTXHVWUDWLRQ VRLO IHUWLOLW\ HQKDQFHPHQW DQG VRLO SROOXWDQW LPPRELOL]DWLRQ %LRFKDU FDQ EH SURGXFHG IURP QDWXUDO IRUHVW ILUHV FDPS ILUHV DQG VWUDZ EXUQLQJ DQG KDV D ORQJ XWLOL]DWLRQ KLVWRU\

7KXV ELRFKDUV DUH XELTXLWRXVO\ SUHVHQW LQ WKH QDWXUDO HQYLURQPHQW ([WHQVLYH

VWXGLHV KDYH LQGLFDWHG WKDW ELRFKDUV IURP GLIIHUHQW S\URO\VLV WHFKQLTXHV DQG GLIIHUHQW SUHFXUVRUV VKRZ GLVWLQFW UHGR[ SURSHUWLHV ELRORJLFDO

QXWULHQW OHDFKLQJ

DQG VRUSWLRQ RI RUJDQLF

VWUXFWXUHV 5HFHQWO\ QDQRSDUWLFOHV

FDUERQ VWDELOLW\ WKHUPRG\QDPLF FKHPLFDO DQG DQG LQRUJDQLF SROOXWDQWV

DQG SHUVLVWHQW IUHH UDGLFDOV

GXH WR WKHLU GLYHUVH

ZHUH JHQHUDWHG DQG GHWHFWHG LQ

ELRFKDUV 6LQFH WKH VWUXFWXUH GHWHUPLQHV WKH IXQFWLRQ DQG DSSOLFDWLRQ RI ELRFKDU

XQGHUVWDQGLQJ RI

ELRFKDU VWUXFWXUHV EHFRPHV D IXQGDPHQWDO LQWHUHVW 7KRXJK ELRFKDU KDV EHHQ XVHG IRU PLOOHQQLD DV D VRLO LQJUHGLHQW WKH VWUXFWXUH RI ELRFKDU UHPDLQV XQFOHDU )RU H[DPSOH &KHQ HW DO SURSRVHG WKDW ELRFKDUV FRQVLVW RI FDUERQL]HG RUJDQLF PDWWHU DQG QRQFDUERQL]HG RUJDQLF PDWWHU ZKLFK FRQWULEXWHV WR WKH DGVRUSWLRQ DQG SDUWLWLRQ PHFKDQLVPV UHVSHFWLYHO\ 7KH SDUWLWLRQ SKDVH WUDQVLWHG WR DGVRUSWLRQ SKDVH ZLWK LQFUHDVLQJ S\URO\VLV WHPSHUDWXUH RI ELRFKDUV IXUWKHU OHDGLQJ WR WKH VRUSWLRQ UDWH YDULHG IURP IDVW WR VORZ DQG WR IDVW DORQJ ZLWK WKH DOWHUDWLRQ RI EL VROXWH VRUSWLRQ DQG WKHUPRG\QDPLF EHKDYLRUV RI ELRFKDUV WRZDUGV RUJDQLF SROOXWDQWV .HLOXZHLW HW DO

LQYHVWLJDWHG WKH G\QDPLF VWUXFWXUHV RI ELRFKDUV XQGHU GLIIHUHQW S\URO\VLV

WHPSHUDWXUHV DQG VXJJHVWHG WKDW ELRFKDU H[SHULHQFHG IRXU GLIIHUHQW SKDVHV GXULQJ S\URO\VLV LQFOXGLQJ WUDQVLWLRQ FKDU DPRUSKRXV FKDU FRPSRVLWH FKDU DQG WXUERVWUDWLF FKDU 7KH RUJDQLF FRPSRQHQWV RI ELRFKDU ZHUH DOVR FODVVLILHG LQWR ZDWHU VROXEOH RUJDQLFV KLJK PROHFXODU ZHLJKW DOLSKDWLFV DQG LQVROXEOH DURPDWLF VWUXFWXUHV

ZKLFK FDQ EH VLPSOLILHG LQWR ODELOH DQG VWDEOH FDUERQ IUDFWLRQV

7KHVH VWXGLHV VKRZHG KHWHURJHQHRXV ELRFKDU SKDVHV LQ GLIIHUHQW ORFDWLRQV EXW ZHUH QRW LQ GHSWK HQRXJK WR FODULI\ WKH PROHFXODU VWUXFWXUH


Page 5 of 27


%DVHG RQ TXDQWLWDWLYH & QXFOHDU PDJQHWLF UHVRQDQFH 105 VSHFWURVFRS\ D PROHFXODU PRGHO RI ELRFKDUV GHULYHG IURP KLJK WHPSHUDWXUH S\URO\VLV ZDV GHWHUPLQHG

5HFHQWO\ ;LDR HW DO SURSRVHG

WKH TXDQWLWDWLYH UHODWLRQ RI UHFWDQJOH OLNH DURPDWLF FOXVWHUV WR WKH VLPSOH SDUDPHWHU RI + & DWRPLF UDWLR RI KLJK WHPSHUDWXUH S\URO\VHG ELRFKDU

DQG WKH SUHGLFWHG VL]H RI WKH DURPDWLF FOXVWHUV ZDV OHVV WKDQ

QP ,W LV ZRUWK QRWLQJ WKDW WKHVH DVVXPHG VWUXFWXUDO PRGHOV ZHUH LQWHJUDWHG PROHFXODU VWUXFWXUHV ZKLFK QHHG PRUH GLUHFW REVHUYDWLRQ 7UDQVPLVVLRQ HOHFWURQ PLFURVFRS\ 7(0 LV D SRZHUIXO WHFKQLTXH ZLWK KLJK UHVROXWLRQ DQG KDV UHFHQWO\ GHYHORSHG DWRPLF UHVROXWLRQ ,W KDV EHHQ ZLGHO\ XVHG IRU FDUERQ PDWHULDO UHVHDUFK VXFK DV IRU DWRPLF GHIHFWV LQ JUDSKHQH

&KHQ HW DO REVHUYHG WKH 7(0 VWUXFWXUH

RI VRRW D FDUERQ PDWHULDO VLPLODU WR ELRFKDU DQG IRXQG DQ RXWHU OD\HU RI DPRUSKRXV FDUERQ ZKLFK FDQ KDUGO\ SURYLGH D FOHDU YLHZ LQWR DURPDWLF FOXVWHUV

0XUDPDWVX HW DO REVHUYHG FOHDU QDQRVL]HG

JUDSKHQH OLNH HGJHV LQ DFWLYDWHG ULFH KXVN ZKLFK DLG LQ DYRLGLQJ FRQGHQVDWLRQ

8QOLNH LQ JUDSKHQH

ZLWK LWV DSSDUHQW FU\VWDOOLQH SURSHUWLHV LW LV YHU\ GLIILFXOW WR REVHUYH DURPDWLF FOXVWHUV LQ KLJK WHPSHUDWXUH S\URO\VLV GHULYHG ELRFKDUV DQG LW LV DOVR KDUG WR SURYH WKH H[LVWHQFH RI WKH QDQRFU\VWDOOLQH DURPDWLF FDUERQ OD\HUHG VWUXFWXUH 7KH PDLQ UHDVRQV DUH DV IROORZV

WKH PLQHUDO FRPSRQHQWV LQ

ELRFKDUV FRXOG HDVLO\ GLVWXUE 7(0 REVHUYDWLRQ EHFDXVH WKH PLQHUDO FRPSRQHQWV XVXDOO\ IRUP PXFK EHWWHU FU\VWDOORLGV WKDQ WKH RUJDQLF FRPSRXQGV LQ ELRFKDUV LQ ELRFKDUV LV VPDOOHU WKDQ PRGHO

WKHRUHWLFDOO\ WKH DURPDWLF FOXVWHU VL]H

QP EDVHG RQ WKH SUHYLRXVO\ UHSRUWHG UHFWDQJOH OLNH DURPDWLF FOXVWHU

DQG DURPDWLF FOXVWHUV RI WKLV VL]H FDQQRW EH REVHUYHG ZLWKRXW KLJK UHVROXWLRQ 7(0 DQG

KLJK WHPSHUDWXUH S\URO\VLV GHULYHG ELRFKDUV DUH FRQVLGHUHG WR KDYH WXUERVWUDWLF KLJKO\ GLVWRUWHG DQG FRQGHQVHG VWUXFWXUHV :LWKRXW VXIILFLHQW GLVSHUVLRQ LW LV KDUG WR DFKLHYH D FOHDU REVHUYDWLRQ RI WKH DURPDWLF FOXVWHUV LQ WKH PROHFXODU VWUXFWXUHV RI ELRFKDUV 7KHUHIRUH ULFH VWUDZ GHULYHG ELRFKDUV S\URO\]HG DW

ƒ& DQG

PLQHUDO FRPSRQHQWV ZHUH UHPRYHG 7KH UHVLGXHV ZHUH QDPHG '56

ƒ& ZHUH SUHSDUHG DQG WKH DQG '56

UHVSHFWLYHO\ DQG

ZHUH WKHQ GLVSHUVHG YLD RUJDQLF VROYHQW H[IROLDWLRQ 7R SURYH WKH H[LVWHQFH RI FOXVWHUHG DURPDWLF VWUXFWXUHV DQG WR PHDVXUH WKH VL]H RI WKHVH DURPDWLF FOXVWHUV LQ WKH H[IROLDWHG ELRFKDUV KLJK UHVROXWLRQ



Page 6 of 27

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

0DWHULDOV DQG 0HWKRGV 3UHSDUDWLRQ RI %LRFKDUV 5LFH VWUDZ ZDV FKRVHQ DV D QDWXUDO VRXUFH RI ELRFKDU GXH WR WKH WUDGLWLRQ RI EXUQLQJ ULFH VWUDZ EDFN WR IDUPODQG LQ &KLQHVH DJULFXOWXUH 7KH ULFH VWUDZ ZDV ULQVHG ILYH WLPHV WR UHPRYH WKH DWWDFKHG GXVW DLU GULHG IRU

GD\V DQG WKHQ RYHQ GULHG RYHUQLJKW DW

ELRPDVV ZDV JURXQG DQG SDVVHG WKURXJK DWPRVSKHUH LQ D SLSH IXUQDFH *6/

PHVK VLHYHV

PP EHIRUH S\URO\VLV XQGHU 1

; +HIHL .HMLQJ 0DWHULDO 7HFKQRORJ\ &R /WG &KLQD 7KH

WHPSHUDWXUH LQ WKH SLSH IXUQDFH ZDV SURJUDPPHG ZLWK D KHDWLQJ UDWH RI WHPSHUDWXUH RI

ƒ& RU

ƒ& IRU

ƒ& 7KH GULHG

ƒ& PLQ DQG KROGLQJ

KRXUV $IWHU FRROLQJ WR URRP WHPSHUDWXUH QDWXUDOO\ ELRFKDUV

FRQWDLQLQJ PLQHUDOV ZHUH REWDLQHG DQG QDPHG 56

DQG 56

LQ ZKLFK WKH VXIIL[ QXPEHU

UHSUHVHQWV WKH S\URO\VLV WHPSHUDWXUH 7R UHPRYH WKH PLQHUDO FRPSRQHQWV +&O DQG +) ZHUH XVHG DFFRUGLQJ WR UHSRUWHG PHWKRGV WKDW FODLPHG WR PDLQWDLQ WKH ELRFKDU RUJDQLF VWUXFWXUH J 56

RU 56

ZDV SODFHG LQWR

P/ SODVWLF FHQWULIXJH WXEHV ZLWK

P/

,Q EULHI

PRO / +&O DQG

VKDNHQ IRU KRXUV 7KHQ WKH VXSHUQDWDQW ZDV UHPRYHG DIWHU FHQWULIXJDWLRQ DW

î J IRU PLQ 7KLV

ZDVKLQJ SURFHVV ZDV UHSHDWHG IRXU WLPHV DQG WKHQ WKH VROXWLRQ ZDV FKDQJHG WR

PRO / +&O

PRO / +) WR UHPRYH VLOLFDWH PLQHUDOV DQG UHSHDWHG IRXU WLPHV $IWHUZDUGV WKH GRXEOH DFLG ZDVKHG VDPSOHV ZHUH ZDVKHG E\ PLOOL 4 ZDWHU XQWLO UHDFKLQJ D QHXWUDO S+ $IWHU RYHQ GU\LQJ RYHUQLJKW DW ƒ& DQG EHLQJ SDVVHG WKURXJK '56

DQG '56

PHVK VLHYHV

PP

WKH ILQDO ELRFKDUV ZHUH ODEHOHG

GRXEOH DFLG WUHDWHG ULFH VWUDZ GHULYHG ELRFKDUV WKH VXIIL[ QXPEHU VWDQGV IRU


Page 7 of 27


WKH SUHSDUDWLRQ WHPSHUDWXUH 6ROYHQW 'LVSHUVHG %LRFKDUV DQG 7(0 2EVHUYDWLRQ 7ZHQW\ ILYH GLIIHUHQW VROYHQWV ZHUH XVHG WR GLVSHUVH '56 RU '56

DQG '56

DFFRUGLQJ WR WKH UHSRUWHG PHWKRG

ZDV DGGHG LQWR D

P/ JODVV ERWWOH ZLWK

7R EH VSHFLILF

PJ '56

P/ VROYHQW $IWHU VRQLFDWLRQ 6.

6KDQJKDL .HGDR 8OWUDVRQLF ,QVWUXPHQW &R 6KDQJKDL &KLQD DW

SRZHU

+3

N+] SRZHU

:

IRU KRXU WKH ERWWOH ZDV WKHQ NHSW VWLOO WR WHVW WKH GLVSHUVLRQ SHUIRUPDQFH DIWHU KRXU DQG GD\V 7KH GLVSHUVHG IUDFWLRQV ZHUH FDOFXODWHG E\ ZHLJKWLQJ WKH VROLG VHGLPHQWV RI WKH ELRFKDUV DIWHU

GD\V RI

VWDQGLQJ VWLOO 7KH VROYHQWV LQFOXGHG PLOOL 4 ZDWHU PHWKDQRO HWKDQRO DFHWRQH WULFKORURPHWKDQH GLFKORURPHWKDQH PHWK\OEHQ]HQH HWK\O DFHWDWH 1 1 GLPHWK\OIRUPDPLGH IRUPDPLGH Q KH[DQH F\FORKH[DQRQH DQLOLQH GLPHWK\OVXOIR[LGH '062 VROXWLRQ FRQWDLQLQJ FKORUREHQ]HQH

PHWK\O

S\UUROLGLQRQH 103 IRUPDOGHK\GH

PHWKDQRO WR SUHYHQW SRO\PHUL]DWLRQ SHWUROHXP HWKHU GLHVHO

DFHWRQLWULOH

GLVSHUVLRQ UHVXOWV RI '56

S\ULGLQH

WHWUDK\GURIXUDQ

DQG '56

WHWUDFKORURPHWKDQH

DUH VKRZQ LQ )LJXUHV

EHQ]HQH

DQG RFWDQRO

7KH

,Q DGGLWLRQ )LJXUH 6 VKRZV WKH

UHODWLRQ EHWZHHQ WKH VROYHQW GHQVLW\ DQG WKH GLVSHUVHG IUDFWLRQ RI '56

DQG '56

ELRFKDUV

7UDQVPLVVLRQ HOHFWURQ PLFURVFRS\ 7(0 FKDUDFWHUL]DWLRQ ZDV FDUULHG RXW DIWHU 103 GLVSHUVLRQ E\ WKH FLWHG PHWKRGV

%ULHIO\

PJ '56

P/ JODVV ERWWOH $IWHU VRQLFDWLRQ DW USP IRU

RU '56 :

PLQ 7(0 REVHUYDWLRQV -(0

N+] IRU

ZDV PL[HG ZLWK

P/ 103 VROYHQW LQ D

PLQ WKH PL[WXUHV ZHUH FHQWULIXJHG DW

-(2/ ZHUH WKHQ PDGH XQGHU

N9 RSHUDWLRQ

DIWHU GURSSLQJ WKH VXSHUQDWDQWV RQWR FDUERQ ILOP FRDWHG FRSSHU PLFURJULGV 7KH +5 7(0 -(0 -(2/ ZDV RSHUDWHG DW

N9 WR REVHUYH WKH EODFN GRWV LQ '56

+5 7(0 )(, 7HFQDL * ) DQDO\VLV +5 7(0 )(, 7LWDQ

DQG '56

VKRZQ LQ )LJXUH

6 7:,1 ZLWK DWWDFKHG ('6 ZDV XVHG IRU IXUWKHU REVHUYDWLRQ DQG ('6 HTXLSSHG ZLWK &V FRUUHFWLRQ ZDV RSHUDWHG DW

DWRPLF UHVROXWLRQ ,Q DGGLWLRQ SRURXV DOXPLQD PHPEUDQHV SRUH VL]H

N9 WR REWDLQ

QP :KDWPDQ ZHUH XVHG WR

YDFXXP ILOWUDWH WKH VXSHUQDWDQWV WR PHDVXUH WKH \LHOG RI QDQRVL]HG ELRFKDUV GLVSHUVHG LQ 103 7KH 7(0 LPDJHV RI JUDSKHQH EHIRUH DQG DIWHU DFLG

GLVSHUVLQJ WUHDWPHQW )LJXUH 6


LQGLFDWHG WKDW WKH


Page 8 of 27

DFLG ZDVKLQJ DQG RUJDQLF VROYHQW GLVSHUVLQJ KDYH OLWWOH HIIHFW RQ WKH VWUXFWXUH RI JUDSKHQH &KDUDFWHUL]DWLRQ RI %LRFKDUV 5DPDQ VSHFWURVFRS\ ZDV FDUULHG RXW WR PHDVXUH WKH JUDSKLWL]LQJ GHJUHH E\ D /DE5$0 +5 89 5DPDQ VSHFWURPHWHU -2ELQ \YRQ )5 ZLWK D ODVHU H[FLWDWLRQ ZDYHOHQJWK RI

QP IURP

FP WR

FP ZLWK D VWHS RI

FP

; UD\ SKRWRHOHFWURQ

VSHFWURVFRS\ ;36 ZDV XVHG WR GHWHUPLQH WKH ERQGLQJ LQIRUPDWLRQ RI FDUERQ LQ ELRFKDUV E\ D 9* (6&$/$% 0$5. ,, ZLWK D VFDQQLQJ VWHS RI

H9 WR REWDLQ & V SHDN VSHFWUD 4XDGUXSROH WLPH RI

IOLJKW PDVV VSHFWURPHWU\ 4 72) DQDO\VLV ZDV FRQGXFWHG LQ SRVLWLYH LRQ PRGH IRU 103 +3/& JUDGH •

GLVSHUVHG ELRFKDUV DIWHU

USP FHQWULIXJDWLRQ (OHPHQWDO DQDO\VLV & + DQG 1 ZDV

FRQGXFWHG E\ DQ HOHPHQWDO DQDO\]HU ($

&+1 7KHUPR )LQQLJDQ

7KH R[\JHQ FRQWHQW ZDV

GHWHUPLQHG E\ PDVV EDODQFH DIWHU DVK FRUUHFWLRQ

5HVXOWV DQG 'LVFXVVLRQ +5 7(0 2EVHUYDWLRQV RI %LRFKDUV 7R VFUHHQ WKH GLVSHUVLRQ DQG H[IROLDWLRQ VROYHQWV WKH GLVSHUVLRQ UHVXOWV RI '56 )LJXUH

DQG '56

LQ

VROYHQWV ZLWK GLIIHUHQW SURSHUWLHV DUH VKRZQ LQ )LJXUH

UHVSHFWLYHO\ $IWHU VRQLFDWLRQ IRU

K WKH '56

GLVSHUVHG LQ PRVW RUJDQLF VROYHQWV EXW DIWHU

DQG '56

PHWK\O

SDUWLFOHV FRXOG EH ZHOO

GD\V RI VHWWOLQJ HWKDQRO WULFKORURPHWKDQH DQG

GLPHWK\OVXOIR[LGH '062 GLVSOD\HG JRRG SHUIRUPDQFH LQ GLVSHUVLQJ '56 WULFKORURPHWKDQH

DQG

SDUWLFOHV ZKLOH ZDWHU

S\UUROLGLQRQH 103 DQG RFWDQRO ZHUH FDSDEOH RI GLVSHUVLQJ '56

7KH GLVSHUVLRQ DELOLW\ RI WKH VROYHQW JHQHUDOO\ GHSHQGV RQ PDQ\ IDFWRUV LQFOXGLQJ WKH GLIIHUHQFH EHWZHHQ WKH ELRFKDU SDUWLFOH GHQVLW\ DQG WKH VROYHQW GHQVLW\ DV ZHOO DV WKH ELRFKDU SDUWLFOH H[IROLDWLRQ DELOLW\ RI WKH VROYHQWV )RU H[DPSOH HWKDQRO DQG '062 FRXOG GLVSHUVH '56

EXW QRW '56

EHFDXVH RI WKH GHQVLW\ GLIIHUHQFH ,W VHHPV WKDW WKH VROYHQW GHQVLW\ GRPLQDWHG WKH ELRFKDU GLVSHUVLRQ DELOLW\ )LJXUH 6

7KH KLJKHVW GHQVLW\ VROYHQW L H

WHWUDFKORURPHWKDQH SURYLGHG WKH ODUJHVW

GLVSHUVHG IUDFWLRQ ,Q DGGLWLRQ WKH GLVSHUVHG IUDFWLRQ RI '56 '56

)LJXUH 6

PHDQLQJ WKDW '56

ZDV JHQHUDOO\ KLJKHU WKDQ WKDW RI

FRQWDLQV PRUH FRQGHQVHG PROHFXODU XQLWV WKDQ '56


Page 9 of 27


)LJXUH

'56

GLVSHUVLRQ UHVXOWV LQ GLIIHUHQW VROYHQWV XQGHU GLIIHUHQW VHWWOHPHQW WLPHV

)LJXUH

'56

GLVSHUVLRQ UHVXOWV LQ GLIIHUHQW VROYHQWV XQGHU GLIIHUHQW VHWWOHPHQW WLPHV



Page 10 of 27

7R REVHUYH VPDOOHU VWUXFWXUHV ELRFKDUV ZHUH H[IROLDWHG E\ 1 PHWK\O

S\UUROLGRQH 103 7KH

103 VROYHQW H[IROLDWLRQ PHWKRG KDV EHHQ ZLGHO\ DSSOLHG WR DFKLHYH KLJK \LHOGV RI JUDSKHQH QDQRVKHHWV IURP VROLG JUDSKLWH DQG EHFDXVH '56

7KH SHUFHQWDJHV RI '56

UHVSHFWLYHO\ 7KH SHUFHQWDJH RI '56

DQG '56

GLVSHUVHG E\ 103 ZHUH

LV VOLJKWO\ KLJKHU WKDQ WKDW RI '56

FRQWDLQV GHQVHU DURPDWLF FOXVWHUV WKDQ '56

GXH WR WKH KLJKHU S\URO\VLV

WHPSHUDWXUH 7KLV LV FRQVLVWHQW ZLWK WKH UHSRUWHG SHUFHQWDJH RI 103 GLVSHUVHG JUDSKHQH IURP JUDSKLWH ZDV RQO\

$OO 7(0 +5 7(0 DQG +5 7(0 ZLWK &V FRUUHFWLRQ LPDJHV LQ WKH FXUUHQW VWXG\

FDPH IURP WKH H[IROLDWHG IUDFWLRQV RI WKH ELRFKDUV E

D

ìXî Ru

G

J

K

íìì vu

H

I

ìXî Ru

)LJXUH

F

ìXí Ru

7KH QDQRFU\VWDO DQG JUDSKLWH FRPSRQHQWV LQ WKH GLVSHUVHG '56

LQGLFDWHG WKH OD\HUHG VWUXFWXUH LQ '56 7KH JUDSKLWH VWUXFWXUHV LQ '56

ELRFKDUV 7KH LPDJHV RI D DQG E

7KH LPDJHV RI H DQG I LQGLFDWHG WKH QDQRFU\VWDO JUDSKHQH VWUXFWXUHV

ZHUH FRQILUPHG E\ WKH VHOHFWHG DUHD HOHFWURQ GLIIUDFWLRQ 6$(' 7KH LPDJHV RI

G DQG K ZHUH WKH FRUUHVSRQGLQJ 6$(' UHVXOWV RI F DQG J DW WKH PLGGOH FHQWHU UHVSHFWLYHO\ 7KH LPDJHV RI D E

H DQG I ZHUH REWDLQHG E\ -(0

7KH VWUXFWXUHV RI '56

ZKLOH WKH LPDJHV RI F

DQG '56

ZLWK D UHVROXWLRQ RI

J DQG K ZHUH REWDLQHG E\ -(0

ZHUH FKDUDFWHUL]HG E\ IRXU GLIIHUHQW W\SHV RI 7(0

LQVWUXPHQWV ZLWK GLIIHUHQW UHVROXWLRQV ZKLFK ZHUH -(0 DQG )(, 7HWDQ

G

-(0 DQG

)(, 7HFQDL * )

QP UHVSHFWLYHO\ -(0

WKH RQO\ LQVWUXPHQW WKDW GRHV QRW KDYH D KLJK UHVROXWLRQ IXQFWLRQ DQG )(, 7HWDQ


6 7:,1 LV

LV WKH RQO\

Page 11 of 27


LQVWUXPHQW WKDW DOORZV IRU &V FRUUHFWLRQ %DVHG RQ WKH 7(0 LPDJHV GHULYHG IURP -(0

)LJXUH

D E H DQG I EXON PXOWL OD\HUHG VWUXFWXUHV JUDSKHQH OLNH DQG QDQRFU\VWDOOLQH VWUXFWXUHV ZHUH REVHUYHG LQ '56

ELRFKDU %\ DSSO\LQJ VHOHFWHG DUHD HOHFWURQ GLIIUDFWLRQ 6$(' WKH JUDSKLWH OLNH

VWUXFWXUHV LQ '56

D

ZHUH FRQILUPHG E\ -(0

'56

E

)LJXUH F G J DQG K QP

F

QP

))7

QP

QP

G

I

H

'56

QP QP

QP

QP

)LJXUH

7(0 LPDJHV RI WKH EODFN GRWV LQ WKH GLVSHUVHG ELRFKDUV E\ -(0

WKH EODFN GRWV LQ WKH GLVSHUVHG '56 LPDJHV RI '56

DQG '56

7KH LPDJHV RI D DQG G VKRZHG

UHVSHFWLYHO\ 3LFWXUHV RI E DQG F VKRZHG WKH +5 7(0

EODFN GRWV 7KH XSSHU ULJKW FRUQHU LPDJH RI F ZDV WKH IDVW )RXULHU WUDQVIRUPDWLRQ ))7 UHVXOWV

RI LPDJH F 3LFWXUHV RI H DQG I VKRZHG WKH +5 7(0 LPDJHV RI '56

EODFN GRWV LQ WKH VDPH ORFDWLRQ EXW ZLWK

GLIIHUHQW GHSWK RI IRFXV

8SRQ IXUWKHU PDJQLILFDWLRQ EODFN GRWV RQ WKH JUDSKHQH OLNH VXUIDFHV RI ERWK WKH GLVSHUVHG '56

DQG '56

ZHUH REVHUYHG LQ )LJXUH D DQG G DQG XQGHU +5 7(0 PRGH RQ -(0

DOPRVW HYHU\ EODFN GRW VKRZHG FU\VWDOOLQH VWULSHV XQGHU FDUHIXO DGMXVWPHQW )LJXUH E DQG F IRU '56

DQG )LJXUH H DQG I IRU '56

)LJXUH H DQG I VKRZV 7(0 LPDJHV WDNHQ DW WKH VDPH

ORFDWLRQ EXW ZLWK D GLIIHUHQW GHSWK RI IRFXV ,QWHUHVWLQJO\ WKH FU\VWDO VWULSHV DSSHDUHG RQ GLIIHUHQW EODFN GRWV VXJJHVWLQJ WKDW WKHVH JUDSKHQH OLNH QDQRVKHHWV ZHUH DUUDQJHG UDQGRPO\ LQ D WXUERVWUDWLF VWDWH 7KH IDVW )RXULHU WUDQVIRUP ))7 UHVXOWV LQ )LJXUH F DUH TXLWH VLPLODU WR WKH UHVXOWV RI EL OD\HU JUDSKHQH



LQ SUHYLRXV ZRUN

PHDQLQJ WKDW WKHVH EODFN GRWV DUH VLPLODU WR JUDSKHQH OLNH VWUXFWXUHV VLQFH FDUERQ

LV GRPLQDQW LQ WKH GLVSHUVHG '56 '56

Page 12 of 27

DQG '56

)XUWKHUPRUH WKH +5 7(0 LPDJHV )LJXUH 6

DW WKH VDPH VHFWLRQ ZLWK D GLIIHUHQW GHSWK RI IRFXV REVHUYHG E\ )(, 7HFQDL * )

RI

6 7:,1

DOVR GLVSOD\HG GLVWLQFW QDQRFU\VWDOOLQH VWULSHV RU HYHQ DWRPLF DUUDQJHPHQWV LQGLFDWLQJ WKH UDQGRP VWDFNLQJ RI WKHVH DURPDWLF FOXVWHUV 7KHVH UHVXOWV LQGLFDWHG WKDW GLIIHUHQW UHVROXWLRQ 7(0 LQVWUXPHQWV FRXOG UHDFK GLIIHUHQW VWUXFWXUDO OHYHOV LQ WKH REVHUYDWLRQ RI ELRFKDUV

D

E

î vu

î vu

F

G

î vu )LJXUH

î vu

+5 7(0 LPDJHV LQ WKH HGJH RI WKH GLVSHUVHG '56

E\ )(, 7LWDQ

E\ )(, 7HFQDL * )

6 7:,1 IRU D DQG E DQG

ZLWK &V FRUUHFWRU IRU F DQG G

6LQFH WKH EODFN GRWV RYHUODSSHG JUHDWO\ LQ WKH PLGGOH RI WKH ELRFKDU VDPSOHV LW ZDV KDUG WR GHILQH WKH VWUXFWXUH RI WKH H[IROLDWHG ELRFKDUV PHUHO\ E\ REVHUYLQJ WKH EODFN GRWV $ QHZO\ LQVWDOOHG )(, 7HFQDL * )

6 7:,1 ZDV XVHG WR REVHUYH WKH HGJH RI WKH GLVSHUVHG ELRFKDU VDPSOHV &V FRUUHFWLRQ

ZDV DSSOLHG E\ )(, 7LWDQ

WR DFKLHYH DWRPLF UHVROXWLRQ )LJXUH

REVHUYHG E\ WKH )(, 7HFQDL * )

6 7:,1 )LJXUH 6

7KH EODFN GRWV ZHUH DOVR

$W WKH HGJH RI WKH GLVSHUVHG ELRFKDUV

DURPDWLF FOXVWHUV DUH FOHDUO\ YLVLEOH )LJXUH E ,Q DGGLWLRQ WR WKH DSSDUHQW


FDUERQ DWRPLF ULQJV

Page 13 of 27


KLJKHU QXPEHUHG FDUERQ DWRPLF ULQJV ZHUH DOVR IRXQG LQ WKH QDQRVWUXFWXUH RI WKH GLVSHUVHG ELRFKDUV DV VKRZQ LQ )LJXUH E 7KLV SKHQRPHQRQ LV LQ DFFRUGDQFH ZLWK WKH ILQGLQJV LQ JUDSKHQH GHIHFWV DQG LV D UHVXOW RI 6WRQH :DOHV WUDQVIRUPDWLRQV ,Q SDUWLFXODU 6WRQH :DOHV WUDQVIRUPDWLRQ FRQWULEXWHV WR WKH IRUPDWLRQ RI FDUERQ QDQRWXEHV IXOOHUHQHV DQG RWKHU FDUERQ QDQRVWUXFWXUHV

7KH NLQG RI 6WRQH :DOHV

WUDQVIRUPDWLRQ WKDW ZH REVHUYHG PD\ EH WKH UHDVRQ ZK\ IXOOHUHQHV FDQ EH IRXQG LQ WKH QDWXUDO HQYLURQPHQW

7R RXU EHVW NQRZOHGJH WKLV LV WKH ILUVW DWRPLF REVHUYDWLRQ RI WKH JUDSKHQH OLNH

VWUXFWXUH RI WKH H[IROLDWHG ELRFKDUV DORQJ ZLWK WKH 6WRQH :DOHV GHIHFWV $URPDWLF &OXVWHU 6WUXFWXUH $QDO\VLV LQ WKH 'LVSHUVHG %LRFKDUV &RPELQLQJ WKH REVHUYDWLRQ RI HGJH DURPDWLF FOXVWHUV LQ )LJXUH DQG EODFN GRWV LQ )LJXUH

WKH VWULSHV DSSHDULQJ RQ WKH EODFN GRWV

LQGLFDWHV DQ RUGHUHG PROHFXODU VWUXFWXUH VLPLODU WR WKH UHSRUWHG VWUXFWXUH RI JUDSKHQH TXDQWXP GRWV DQG R[LGDWLRQ GHEULV RQ WKH VXUIDFH RI JUDSKHQH R[LGH QDQRVKHHWV VPDOOHU WKDQ QP DQG

QP LQ VL]H DQG WKH DYHUDJH VL]HV RI '56

7KH EODFN GRWV DUH JHQHUDOO\

DQG '56

ZHUH PHDVXUHG WR EH

QP UHVSHFWLYHO\ )LJXUH E DQG H 5HFHQWO\ D TXDQWLWDWLYH UHODWLRQVKLS PRGHO ZDV

HVWDEOLVKHG EHWZHHQ WKH VL]H RI WKH DURPDWLF VWUXFWXUHV DQG WKH + & UDWLR RI ELRFKDUV + & UDWLR RI '56 '56

DQG '56

DQG '56

7DEOH 6

%DVHG RQ WKH

WKH VL]H RI WKH DURPDWLF FOXVWHUV LQ

LV FDOFXODWHG WR EH DSSUR[LPDWHO\ î DQG î EHQ]HQH ULQJV LQ D UHFWDQJXODU

DUUD\ UHVSHFWLYHO\ ZKLFK PHDQV WKH FRUUHVSRQGLQJ WKHRUHWLFDO VL]H LV VL]H RI EHQ]HQH ULQJV LQ JUDSKHQH QDQRVKHHWV LV DSSUR[LPDWHO\

QP DQG QP

QP DV WKH

7KH PHDVXUHG VL]H RI WKH

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




Page 14 of 27

Page 15 of 27


7KH VWUXFWXUDO GLVWDQFH DQDO\VLV RI WKH GLVSHUVHG '56

DQG '56

LV JLYHQ LQ )LJXUH

,Q WKH

WKHRUHWLFDO VWUXFWXUH PRGHO RI JUDSKLWH )LJXUH F WKH & & ERQG GLVWDQFH OD\HU GLVWDQFH DGMDFHQW EHQ]HQH ULQJ GLVWDQFH DQG WKH VWULSH GLVWDQFH DUH

DQG

QP UHVSHFWLYHO\

7KHVH GLVWDQFHV DUH OLQHDUO\ UHODWHG WR HDFK RWKHU ,Q WKH +5 7(0 LPDJHV REWDLQHG E\ )(, 7HFQDL * )

6 7:,1 WKH PHDVXUHG VWULSH GLVWDQFH RI WKH GLVSHUVHG '56

ZKLOH WKH PHDVXUHG DGMDFHQW EHQ]HQH ULQJ GLVWDQFH RI '56 RI WKH GLVSHUVHG '56

DQG '56

LV

LV

QP )LJXUH D

QP )LJXUH E %RWK GLVWDQFH

DUH YHU\ FORVH WR WKH WKHRUHWLFDO GLVWDQFH RI JUDSKLWH IXUWKHU

SURYLQJ WKDW WKH VWULSHV DQG EHQ]HQH ULQJV RI WKH GLVSHUVHG '56 FOXVWHUV 0RUHRYHU EDVHG RQ WKH VWULSH GLVWDQFH RI '56 WKH & & ERQGLQJ OHQJWKV DUH FDOFXODWHG WR EH

DQG '56

EHORQJ WR DURPDWLF

DQG WKH EHQ]HQH ULQJV GLVWDQFH RI '56 DQG

QP UHVSHFWLYHO\ ,Q JHQHUDO WKH

VWDQGDUG & & VLQJOH ERQG & & GRXEOH ERQG & & WULSOH ERQG DQG & & DURPDWLF ERQG OHQJWKV DUH DQG

QP UHVSHFWLYHO\ 7KH & WR & ERQG OHQJWKV LQ '56

DQG '56

DUH

EHWZHHQ WKH & & VLQJOH ERQG DQG & & GRXEOH ERQG OHQJWK ZKLFK PHDQV WKDW WKH FDUERQ VWUXFWXUH RI '56

DQG '56

LV DURPDWLF ,Q DGGLWLRQ WKH & & OHQJWK RI '56

LV ORZHU WKDQ WKDW RI '56

LQGLFDWLQJ WKDW GXULQJ S\URO\VLV WKH & & OHQJWK WUDQVLWLRQV IURP DOLSKDWLF WR DURPDWLF ZLWK LQFUHDVLQJ S\URO\VLV WHPSHUDWXUH 'XH WR WKH LQDFFXUDF\ RI R[\JHQ FRQWHQW GHULYHG IURP WKH HOHPHQWDO DQDO\VLV

;36 VSHFWUD ZHUH

XVHG WR SUREH WKH FRPSRVLWLRQ RI WKH ELRFKDUV DQG WR FDOFXODWH WKH UDWLR RI R[\JHQ DQG FDUERQ ZKLFK ZDV PXFK PRUH VWUDLJKW IRUZDUG GHVSLWH RI WKH VHPL TXDQWLILFDWLRQ RI ;36 GDWD ;36 LV D VXUIDFH VHQVLWLYH TXDQWLWDWLYH VSHFWURVFRSLF WHFKQLTXH WKDW FRXOG GLUHFWO\ PHDVXUH WKH HOHPHQWDO FRPSRVLWLRQ EDVHG RQ WKH GLIIHUHQW HVFDSH HQHUJ\ RI HOHFWURQV LQ GLIIHUHQW NLQGV RI DWRPV 7KH DWRPLF VHQVLWLYLW\ IDFWRUV RI R[\JHQ DWRP

V LV

PXFK KLJKHU WKDQ WKH

IRU FDUERQ DWRPV

PHDQLQJ WKDW ;36

VLJQDO LV PRUH VHQVLWLYH WR R[\JHQ WKDQ FDUERQ 7KHUHIRUH 2 & DWRPLF UDWLR UHVXOWV IURP ;36 PD\ EH PRUH UHOLDEOH WKDQ WKH HOHPHQWDO DQDO\VLV 7KH FDUERQ DQG R[\JHQ HOHPHQWV DUH GRPLQDQW LQ WKH ELRFKDUV )LJXUH

$V FDQ EH VHHQ IURP WKH & V VSHFWUD LQ )LJXUH E DQG G WKH SUHGRPLQDQW FDUERQ



LQ '56

DQG '56

LV & & & & DW

Page 16 of 27

H9 %DVHG RQ WKH DUHD RI WKH & V ILWWHG SHDN DQG WKH 2

V ILWWHG SHDN GDWD QRW VKRZQ WKH 2 & DWRPLF UDWLR ZDV FDOFXODWHG WR EH

DQG

IRU

'56

DQG '56

UHVSHFWLYHO\ LQGLFDWLQJ D KLJK DPRXQW RI FDUERQ FRPSRVLWH LQ '56

DQG

'56

5DPDQ PHDVXUHPHQWV ZHUH DOVR FDUULHG RXW WR FKDUDFWHUL]H WKH TXDOLW\ RI WKH DURPDWLF FOXVWHU

VWUXFWXUH RI ELRFKDUV )LJXUH D 7KH * SHDN UHSUHVHQWV WKH KLJK IUHTXHQF\ ( J SKRQRQ DW WKH %ULOORXLQ ]RQH FHQWHU + ZKLOH WKH ' SHDN LV FDXVHG E\ WKH EUHDWKLQJ PRGHV RI VL[ DWRP EHQ]HQH ULQJV DQG UHTXLUHV D GHIHFW IRU LWV DFWLYDWLRQ

7KHUHIRUH WKH ' EDQG LV XVXDOO\ FRQVLGHUHG WR RULJLQDWH IURP WKH

VWUHWFKLQJ YLEUDWLRQ RI VS FDUERQ DWRPV ZKLFK LQGLFDWHV GHIHFWV DQG GLVRUGHUV RI JUDSKHQH QDQRVKHHWV ZKLOH WKH * EDQG RULJLQDWHV IURP WKH VWUHWFKLQJ YLEUDWLRQ RI VS FDUERQ DWRPV ZKLFK LQGLFDWHV WKH FU\VWDOOLQLW\ RI JUDSKHQH QDQRVKHHWV 7KH ' EDQG DW REVHUYHG LQ WKH VSHFWUD RI ERWK '5

DQG '56

FP DQG * EDQG DW ZLWK ,' ,* UDWLRV RI

DQG

FP ZHUH UHVSHFWLYHO\

7KHVH ,' ,* UDWLRV ZKLFK UHIHU WR WKH GHJUHH RI GHIHFWV LQ WKH FDUERQ PDWHULDO DUH PXFK ORZHU WKDQ WKH UHSRUWHG UDWLRV IURP K\GURWKHUPDOO\ V\QWKHVL]HG JUDSKHQH TXDQWXP GRWV DQG DUH VOLJKWO\ KLJKHU WKDQ WKH UDWLRV RI HOHFWURFKHPLFDOO\ SUHSDUHG JUDSKHQH TXDQWXP GRWV

LQGLFDWLQJ WKDW WKH JUDSKHQH

TXDQWXP GRW OLNH VWUXFWXUH LV SUHVHQW LQ WKH ELRFKDUV 0RUHRYHU WKH ,' ,* RI '56 WKDQ WKDW RI '56

LV VOLJKWO\ ORZHU

ZKLFK LV SRVVLEO\ GXH WR WKH IDFW WKDW KLJKHU WHPSHUDWXUH S\URO\VLV FDQ LQGXFH

FDUERQ GLVORFDWLRQ WR JHQHUDWH GHIHFWV PRUH HDVLO\


Page 17 of 27


)LJXUH DQG '56

5DPDQ VSHFWUD D ;36 VSHFWUD F RI '56

DQG '56

ELRFKDUV 7KH & V SHDN VSHFWUD RI '56

ZHUH GHPRQVWUDWHG LQ E DQG G UHVSHFWLYHO\

4XDWHUQDU\ 6WUXFWXUH RI %LRFKDU 3DUWLFOHV 4XDGUXSROH WLPH RI IOLJKW PDVV VSHFWURPHWU\ 4 72) LV D XVHIXO WRRO WR DQDO\]H WKH PROHFXODU VWUXFWXUH RI FDUERQ PDWHULDOV ,Q LGHQWLILHG E\ WLPH RI IOLJKW PDVV VSHFWURPHWU\

LV PHDVXUHG WR EH

LV

WKH KLJKHVW P ] LQ WKH

D P X ZLWK D VLQJOH FKDUJH ZKLOH WKH KLJKHVW P ] RI '56

D P X ZLWK D GRXEOH FKDUJH 7KHVH UHVXOWV LQGLFDWHG WKDW WKH PD[LPDO

PROHFXODU PDVV ZHLJKW LV GLVSHUVHG '56

ZDV ILUVW

+HUH 4 72) ZDV HPSOR\HG LQ SRVLWLYH LRQ PRGH WR

SUREH WKH PDVV ZHLJKW RI 103 GLVSHUVHG ELRFKDUV $V VKRZQ LQ )LJXUH GLVSHUVHG VROXWLRQ RI '56

&

DQG '56

D P X DQG

D P X IRU WKH JUDSKHQH OLNH QDQRVKHHWV LQ WKH

UHVSHFWLYHO\ ZKLFK LV LQ H[FHOOHQW DJUHHPHQW WR WKH PRGHO VWUXFWXUH

DFFRUGLQJ WR WKH TXDQWLWDWLYH UHODWLRQ EHWZHHQ WKH + & UDWLR DQG WKH VWUXFWXUH




Page 18 of 27

Page 19 of 27




Page 20 of 27

WKHVH GLIIHUHQW FDUERQ SKDVHV FRQQHFWHG WR HDFK RWKHU ,Q FRQFOXVLRQ ZH IRU WKH ILUVW WLPH UHSRUW KLJK TXDOLW\ LPDJLQJ RI WKH DURPDWLF FOXVWHU VWUXFWXUH RI KLJK WHPSHUDWXUH S\URO\VLV GHULYHG ELRFKDUV E\ +5 7(0 )XUWKHU ;36 5DPDQ DQG 4 72) FKDUDFWHUL]DWLRQ RI WKH ELRFKDUV FRQILUPV WKH KLJK TXDOLW\ RI WKH DURPDWLF FOXVWHUV LQ WKH 103 GLVSHUVHG '56

DQG '56

7KH ILQH DWRPLF VWUXFWXUH RI ELRFKDUV FRQWDLQV D VHULHV RI GLIIHUHQW

PROHFXOHV DQG ZLOO KHOS XV LOOXVWUDWH WKH SURSHUWLHV RI ELRFKDUV LQFOXGLQJ EXW QRW OLPLW WR WKH FKHPLFDO LQHUWQHVV WR[LFLW\ RSWLFDO DQG HOHFWURQLF SURSHUWLHV DQG FRQGXFWLYLW\ 7KH VXJJHVWHG *DXVVLDQ GLVWULEXWLRQ PRGHO ZLWKLQ WKH ELRFKDUV VKRZV WKH UDWLRQDOLW\ RI SUHYLRXV SKDVH GHILQLWLRQV RI ELRFKDUV VXFK DV KDUG DQG VRIW FDUERQ FDUERQL]HG DQG QRQFDUERQL]HG RUJDQLF PDWWHU DQG ODELOH DQG VWDEOH FDUERQ DQG H[SODLQHG ZK\ 3$+V FRXOG EH H[WUDFWHG IURP ELRFKDUV

DQG ZK\ EXON JUDSKLWH OLNH

VWUXFWXUHV ZHUH REVHUYHG 7KH TXDWHUQDU\ VWUXFWXUH RI ELRFKDUV ZDV SURSRVHG IRU WKH ILUVW WLPH ,Q DGGLWLRQ DURPDWLF FOXVWHUV LQ WKH GLVSHUVHG ELRFKDUV SURYLGHG D QDWXUDO VRXUFH RI JUDSKHQH QDQRVKHHWV WKDW PD\ WUDQVSRUW HOHFWURQV LI ELRFKDU ZDV QDQRVL]HG 7KH UHFHQWO\ GLVFRYHUHG SHUVLVWHQW IUHH UDGLFDOV LQ ELRFKDUV PD\ DOVR EH SDUW RI RU DW OHDVW DWWDFKHG WR WKH ELRFKDU DURPDWLF FOXVWHUV $OWKRXJK WKH 103 GLVSHUVHG IUDFWLRQ RI ELRFKDUV SRVVHVVHG RQO\

DQG

RI '56

DQG '56

UHVSHFWLYHO\

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

$662&,$7(' &217(17 6XSSRUWLQJ ,QIRUPDWLRQ


Page 21 of 27


7KH HOHPHQWV DQDO\VLV UHVXOWV RI '56

DQG '56

VROYHQWV GHQVLW\ DQG GLVSHUVHG IUDFWLRQV RI '56

DUH JLYHQ LQ 7DEOH 6 DQG '56

7KH UHODWLRQVKLS RI

DUH SUHVHQWHG LQ )LJXUH 6

LPDJHV RI JUDSKHQH EHIRUH DQG DIWHU VDPSOH WUHDWPHQW ZHUH SUHVHQWHG LQ )LJXUH 6 LPDJHV RI WKH GLVSHUVHG '56 7HFQDL * ) '56

WKH +5 7(0

DW WKH VDPH VHFWLRQ ZLWK GLIIHUHQW GHSWK RI IRFXV REVHUYHG E\ )(,

6 7:,1 DUH SUHVHQWHG LQ )LJXUH 6

DQG WKH VWULSHV LQ WKH HGJH RI '56

LQ )LJXUH 6

7(0

WKH EODFN GRWV RI WKH GLVSHUVHG '56

REVHUYHG E\ )(, 7HFQDL * )

PRUH GHWDLOHG 4 72) VSHFWUD RI '56

DQG '56

DQG

6 7:,1 DUH SUHVHQWHG

DUH SUHVHQWHG LQ )LJXUH 6

7KLV

LQIRUPDWLRQ LV DYDLODEOH IUHH RI FKDUJH YLD WKH ,QWHUQHW DW KWWS SXEV DFV RUJ

$87+25 ,1)250$7,21 &RUUHVSRQGLQJ $XWKRU 3KRQH

ID[

H PDLO EOFKHQ#]MX HGX FQ

1RWHV 7KH DXWKRUV GHFODUH QR FRPSHWLQJ ¿QDQFLDO LQWHUHVW

$FNQRZOHGJHPHQWV 7KLV SURMHFW ZDV VXSSRUWHG E\ WKH 1DWLRQDO 1DWXUDO 6FLHQFH )RXQGDWLRQV RI &KLQD *UDQW DQG

WKH 1DWLRQDO %DVLF 5HVHDUFK 3URJUDP RI &KLQD *UDQW

DQG WKH 1DWLRQDO .H\ 7HFKQRORJ\ 6XSSRUW 3URJUDP RI &KLQD

&%

%$& %

5HIHUHQFHV /HKPDQQ - $ KDQGIXO RI FDUERQ 1DWXUH &KHQ % =KRX ' =KX / 7UDQVLWLRQDO DGVRUSWLRQ DQG SDUWLWLRQ RI QRQSRODU DQG SRODU DURPDWLF FRQWDPLQDQWV E\ ELRFKDUV RI SLQH QHHGOHV ZLWK GLIIHUHQW S\URO\WLF WHPSHUDWXUHV (QYLURQ 6FL 7HFKQRO

±

:RROI ' $PRQHWWH - ( 6WUHHW 3HUURWW ) $ /HKPDQQ - -RVHSK 6 6XVWDLQDEOH ELRFKDU WR PLWLJDWH JOREDO FOLPDWH



FKDQJH 1DW &RPPXQ 5HQQHU 5 5HWKLQNLQJ ELRFKDU (QYLURQ 6FL 7HFKQRO *ODVHU % 3DUU 0 %UDXQ & .RSROR * %LRFKDU LV FDUERQ QHJDWLYH 1DW *HRVFL +D\HV 0 + % %LRFKDU DQG ELRIXHOV IRU D EULJKWHU IXWXUH 1DWXUH 6RKL 6 3 &DUERQ VWRUDJH ZLWK EHQHILWV 6FLHQFH %HHVOH\ / 0RUHQR -LPHQH] ( *RPH] (\OHV - / +DUULV ( 5RELQVRQ % 6L]PXU 7 $ UHYLHZ RI ELRFKDUV SRWHQWLDO UROH LQ WKH UHPHGLDWLRQ UHYHJHWDWLRQ DQG UHVWRUDWLRQ RI FRQWDPLQDWHG VRLOV (QYLURQ 3ROOXW

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


Page 22 of 27

Page 23 of 27


+DOH 6 ( +DQOH\ . /HKPDQQ - =LPPHUPDQ $ 5 &RUQHOLVVHQ * (IIHFWV RI FKHPLFDO ELRORJLFDO DQG SK\VLFDO DJLQJ DV ZHOO DV VRLO DGGLWLRQ RQ WKH VRUSWLRQ RI S\UHQH WR DFWLYDWHG FDUERQ DQG ELRFKDU (QYLURQ 6FL 7HFKQRO

&KHQ % &KHQ = 6RUSWLRQ RI QDSKWKDOHQH DQG

QDSKWKRO E\ ELRFKDUV RI RUDQJH SHHOV ZLWK GLIIHUHQW S\URO\WLF

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

$ELYHQ 6 6FKPLGW 0 : , /HKPDQQ - %LRFKDU E\ GHVLJQ 1DW *HRVFL &KHQ = &KHQ % &KLRX & 7 )DVW DQG VORZ UDWHV RI QDSKWKDOHQH VRUSWLRQ WR ELRFKDUV SURGXFHG DW GLIIHUHQW



WHPSHUDWXUHV (QYLURQ 6FL 7HFKQRO

±

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

&KHQ % +XDQJ : (IIHFWV RI FRPSRVLWLRQDO KHWHURJHQHLW\ DQG QDQRSRURVLW\ RI UDZ DQG WUHDWHG ELRPDVV JHQHUDWHG VRRW RQ DGVRUSWLRQ DQG DEVRUSWLRQ RI RUJDQLF FRQWDPLQDQWV (QYLURQ 3ROOXW 0XUDPDWVX + .LP < $

A Direct Observation of the Fine Aromatic Clusters and Molecular

Recommend Documents