conformational specific spectroscopy of jet cooled 3-(4-hydroxyphenyl)-n-benzyl- propionamide...
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![Page 1: CONFORMATIONAL SPECIFIC SPECTROSCOPY OF JET COOLED 3-(4-HYDROXYPHENYL)-N-BENZYL- PROPIONAMIDE (HNBPA) ESTEBAN E. BAQUERO, V. ALVIN SHUBERT, AND TIMOTHY](https://reader036.vdocument.in/reader036/viewer/2022070411/56649f3e5503460f94c5ea20/html5/thumbnails/1.jpg)
CONFORMATIONAL SPECIFIC SPECTROSCOPY OF JET COOLED 3-(4-HYDROXYPHENYL)-N-BENZYL-
PROPIONAMIDE (HNBPA)
ESTEBAN E. BAQUERO, V. ALVIN SHUBERT, AND TIMOTHY ZWIER Department of Chemistry, Purdue University
West Lafayette, IN 47907
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N
HO
OH
N
H
O
OH
IntroductionIntroduction
Motivation
- Learn about Electronic Energy Transfer (EET)
- Test Theories of Fluorescence Resonant Energy Transfer (FRET) measurements - Conformational specific spectroscopy allows us to test chromophoric distance and orientation dependence of EET. - Dispersed fluorescence measurements can be used to measure conformational efficiency of EET.
HNBPA
Flexible
Rigid
DeMember JR, Filipescu N. J. Am.Chem. Soc. 90, 6425 (1968)
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Experimental methodsResonant 2 photon ionization (R2PI): Records spectra in mass selective fashion
Biomolecule* (S1)
Biomolecule (S0)
Biomolecule+ + e-
Hol
e-bu
rn
Pro
be
Conformer A Conformer B
Hol
e-bu
rn
Pro
be
R2PI: Electronic SpectrumUV-UV Hole-burning: Conformation
specific electronic spectrum
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4
3
2
1
36000359003580035700356003550035400
P-Cresol35338 cm-1
R2PI Spectrum of HNBPAR2PI Spectrum of HNBPA
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UV-UV Hole-burning Spectra of HNBPAUV-UV Hole-burning Spectra of HNBPA -Two major conformers and one minor were found
14
12
10
8
6
4
2
0
Ion
Inte
nsity
(arb
itrar
y un
its)
3740037200370003680036600364003620036000358003560035400Photo Energy (cm
-1)
R2PI HNBPA
HB at 3567 cm-1
(also origin)
HB at 35517 cm-1
(origin at 35368 cm-1
)
P-Cresol 35338 cm-1 Toluene 37477.4 cm-1
B
A
HB at 35670 cm-1 (also origin)
HB at 35517 cm-1 (origin at 35368)
Minor Conformer
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Laser Induced Fluorescence Spectrum of p-cresol
I Appel, K. Kleinermanns Ber Busenges. Phys. Chem. 91, 140-152 (1987)
CH3
OH
N
H
O
OH
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UV-UV Hole-burning Spectra of HNBPAUV-UV Hole-burning Spectra of HNBPA
12
10
8
6
4
2
0
Ion
Inte
nsity
(arb
itrar
y un
its)
3740037200370003680036600364003620036000358003560035400Photo Energy (cm
-1)
HB at 35670 cm-1
(also origin)
HB at 35517 cm-1
(origin at 35368 cm-1
)
Origin 400 cm-1
800 cm-1
1238 cm-1
1600 cm-1
Origin440 cm
-1
800 cm-1
1270 cm-1
6a10 121
0 6a20 122
0
6a10 121
0 6a20
S2 0 00
Toluene-like origin
Photon Energy (cm-1)
A
B
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UV-UV Hole-burning Origin Region
-4
-2
0
2
4
ion
inte
nsity
(ar
bitr
ary
units
)
36000359003580035700356003550035400photon energy (cm
-1)
0 28
4571 87
97
111149
202
016
38
52/54
70/74
127
137
164 1
74 18
8
31/3
4
A
B
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R2PI Showing Progressions of Conformer A
0.15
0.10
0.05
0.00
-0.05
ion
inte
nsity
(ar
bitr
ary
units
)
35520355003548035460354403542035400353803536035340Photon energy (cm
-1)
0
28
45
55
71 87
97
111
128137
45 42 41
28 27
26 26 26
26
124.
5
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10.54 cm10.54 cm-1-1
20.10 cm20.10 cm-1-1
31.16 cm31.16 cm-1-1
38.80 cm38.80 cm-1-1
48.74 cm48.74 cm-1-1
66.29 cm66.29 cm-1-1
113.36 cm113.36 cm-1-1
9.69 cm9.69 cm-1-1
21.38 cm21.38 cm-1-1
31.35 cm31.35 cm-1-1
37.43 cm37.43 cm-1-1
49.56 cm49.56 cm-1-1
65.74 cm65.74 cm-1-1
100.25 cm100.25 cm-1-110.60 cm10.60 cm-1-1
18.07 cm18.07 cm-1-1
23.36 cm23.36 cm-1-1
31.29 cm31.29 cm-1-1
38.02 cm38.02 cm-1-1
57.62 cm57.62 cm-1-1
70.80 cm70.80 cm-1-1 9.62 cm9.62 cm-1-1
16.32 cm16.32 cm-1-1
22.67 cm22.67 cm-1-1
31.55 cm31.55 cm-1-1
40.43 cm40.43 cm-1-1
60.05 cm60.05 cm-1-1
74.77 cm74.77 cm-1-1
Fundamentals
Conformer A
28cm-1 45 cm-1 111cm-1
Conformer B
16cm-1 34cm-1 38cm-1
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So Resonant Ion-dip Infrared Spectroscopy (RIDIRS)
Biomolecule *(S1)
Biomolecule+ + e-
Biomolecule (A) NH or OH stretch
(S0, v=1)
UV Source fixed: Provides selectivity IR Source tuned
Laser Timing
50-200nsec
IRHole-burn
UVprobe
Active Baseline Subtraction
3000 3200 3400 3600 3800Wavenumbers (cm-1)
SubtractedSignal
UV only
UV +IR
Difference
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IR Spectra of HNBPAIR Spectra of HNBPA
0.4
0.3
0.2
0.1
0.0
-0.1
-0.2Inte
nsi
ty (
Fra
ctio
nal
Dep
leti
on
)
370036803660364036203600Wavenumbers (cm
-1)
Conformer B
Conformer A
1.0
0.5
0.0
-0.5
Inte
nsi
ty (
Fra
ctio
nal
Dep
leti
on
)
350034903480347034603450Wavenumbers (cm
-1)
Conformer A
Conformer B
N-H Stretch Region O-H Stretch Region
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Calculated Structures for HNBPACalculated Structures for HNBPA-Conformational search is done using AMBER force field in MacroModel package.
- DFT calculations are then made using Gaussian03 at the B3LYP/6-31+G* level.
0.393 kcal/mol
0.313 kcal/mol0.000 kcal/mol
0.143 kcal/mol 0.884 kcal/mol
0.882 kcal/mol0.315 kcal/mol
0.400 kcal/mol
Folded Perpendicular (FP) Extended Facing (EF) Extended Perpendicular (EP) Folded Facing (FF)
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Calculated IR Hydride Stretch RegionCalculated IR Hydride Stretch Region
0.000 kcal/mol
0.313 kcal/mol
0.882 kcal/mol
300
250
200
150
100
50
0
Infra
red
Inte
nsity
(KM
/mol
e)
376037403720370036803660364036203600Frequency (cm
-1)
300
250
200
150
100
50
0
Infra
red
Inte
nsity
(KM
/mol
e)
376037403720370036803660364036203600Frequency (cm
-1)
0.315 kcal/mol
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UV-UV Hole-burning Spectra of HNBPAUV-UV Hole-burning Spectra of HNBPA
12
10
8
6
4
2
0
Ion
Inte
nsity
(arb
itrar
y un
its)
3740037200370003680036600364003620036000358003560035400Photo Energy (cm
-1)
HB at 35670 cm-1
(also origin)
HB at 35517 cm-1
(origin at 35368 cm-1
)
Origin 400 cm-1
800 cm-1
1238 cm-1
1600 cm-1
Origin440 cm
-1
800 cm-1
1270 cm-1
6a10 121
0 6a20 122
0
6a10 121
0 6a20
S2 0 00
Toluene-like origin
Photon Energy (cm-1)
A
B
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Summary
EvidenceEvidence Conformer AConformer A Conformer BConformer B
UV SpectrumUV Spectrum FPFP EP>EF≈FFEP>EF≈FF
IR SpectrumIR Spectrum FPFP FF>EPFF>EP
SS22 0 00000 FFFF EP>EF≈FFEP>EF≈FF
Tentative Tentative AssignmentAssignment FPFP EPEP
Folded Perpendicular (FP) Extended Facing (EF) Extended Perpendicular (EP) Folded Facing (FF)
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Future WorkFuture Work
-Conformational assignments by double resonant IR-microwave spectroscopy (collaboration with Brian Dian and Brooks Pate at the University of Virginia). TA06, TA07, TA08, TI09, TI11, RI06, FC03, FC04.
- Dispersed fluorescence spectra will be taken in order to probe (EET) and its conformational dependence.
- New systems will be studied such as:
N-Z-L Serine benzyl ester
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ConclusionsConclusions
- Electronic energy transfer could be tested in bichromophore systems such as HNBPA were the system’s flexibility allows the sampling of many distances and orientations between chromophores.
- HNBPA may already show evidence for conformational dependence (EET), which needs further study.
N
HO
OH
N
H
O
OH
HNBPA
Flexible
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AcknowledgementsAcknowledgements
PeoplePeople Prof. Timothy S. ZwierProf. Timothy S. Zwier
The Zwier GroupThe Zwier Group Alvin Shubert Alvin Shubert Jasper ClarksonJasper Clarkson
Tracy LeGreveTracy LeGreveWilliam “Bill” JamesWilliam “Bill” JamesJaime StearnsJaime StearnsNathan PillsburyNathan PillsburyJosh NewbyJosh NewbyTalitha SelbyTalitha Selby
FundingFundingNational Science FoundationNational Science Foundation