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Laser spectroscopic study of estrogen and its hydrated clusters in a supersonic jet ○ Fumiya Morishima, Yoshiya Inokuchi, Takayuki Ebata Graduate School.

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Presentation on theme: "Laser spectroscopic study of estrogen and its hydrated clusters in a supersonic jet ○ Fumiya Morishima, Yoshiya Inokuchi, Takayuki Ebata Graduate School."— Presentation transcript:

1 Laser spectroscopic study of estrogen and its hydrated clusters in a supersonic jet ○ Fumiya Morishima, Yoshiya Inokuchi, Takayuki Ebata Graduate School of Science, Hiroshima Univ.

2 Introduction A D D Fukuzawa et al. Journal of Computational Chemistry In estrogen receptor Cegelski et al. Drug Development Research In membrane estriol(E 3 ) A D estrone(E 1 ) A D β-estradiol(E 2 ) A D estrogen B C B C B C 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 3 16 17 3 16 17

3 Introduction Investigate the structure of bare estrogen and its hydrated clusters to clarify their hydrogen bonding ability. estriol(E 3 ) A D estrone(E 1 ) A D β-estradiol(E 2 ) A D estrogen B C B C B C 3 16 17 3 16 17 3 16 17

4 Experimental and Computational vacuum chamber He gas IR laser UV laser ~4 atm Supersonic jet Vacuum chamber heater temperature estrone : ~150 ℃ estradiol : ~130 ℃ estriol : ~190 ℃ Electronic spectra LIF To differentiate bands UV-UV hole-burning(HB) Vibrational spectra IR-UV double resonance experimental Quantum chemical calculation M05-2X / 6-311++G**

5 S 1 -S 0 Electronic Spectra of Bare Estrogen a bc d 1 2 1 2 3 4 5 6 7 8 9 UV wavenumber / cm -1 LIF and UV-UV HB spectra of bare estrogen Number of conformer = 4 = 6 or more? = 2 Each conformer of estrogen originates from orientation of OH group(s) estrone estradiol estriol

6 IR Spectra of Bare Estrone UV wavenumber / cm -1 1 2 1 2 3657 3658 IR wavenumber / cm -1 IR spectra in the region of OH stretching vibration IR spectra in the region of OH stretching vibration cis-estrone trans-estrone estrone(E 1 ) cis-estrone trans-estrone A D Number of conformer = 2 LIF

7 cis-estrone 1 2 UV wavenumber / cm -1 Assignment for cis- and trans- Conformation of Estrone trans-estrone Comparison of LIF spectra of estrone and results of TD-DFT calculation Comparison of LIF spectra of estrone and results of TD-DFT calculation cis-estrone trans-estrone

8 a bc d 1 2 1 2 3 4 5 6 7 8 9 UV wavenumber / cm -1 estrone estradiol estriol Assignment for cis- and trans- Conformation of Estrogen cis-trans-

9 IR Spectra of Bare Estradiol UV wavenumber / cm -1 a b c d a b c d IR wavenumber / cm -1 β-estradiol(E 2 ) 3656 3655 3657 3658 3642 3641 A-ring OH D-ring OH A-ring OH stretching vibrations… a, c show two bands b, d show only one band. A D estrone(E 1 ) A D IR spectra in the region of OH stretching vibration IR spectra in the region of OH stretching vibration Number of conformer = 4 cis- trans- LIF

10 16 17 Conformations of A-ring & D-ring anti: ~14cm -1 gauche(+): 0cm -1 gauche(-): ~73cm-1 cis trans anti gauche(+)

11 antigauche(+) Four conformers cis trans anti gauche(+) × Conformations of A-ring & D-ring 16 17

12 Assignment of D-ring OH Conformations a b c d IR wavenumber / cm -1 UV wavenumber / cm -1 a : anti b : gauche(+) c : anti d : gauche(+) 3656 3655 36573658 3642 3641 cis -anti trans -gauche(+) cis -gauche(+) trans -anti

13 d: trans -gauche(+) b: cis -gauche(+) a: cis -anti c: trans -anti a b c d cis -anti trans -gauche(+) cis -gauche(+) trans -anti Assignment of bare estradiol

14 With water vapor Without water vapor Hydrated Cluster of Estradiol on A-ring UV wavenumber / cm -1 A B C D a b c d LIF and UV-UV HB spectra of monohydrated cluster of estradiol LIF and UV-UV HB spectra of monohydrated cluster of estradiol β-estradiol(E 2 ) Red shift = 350 cm -1 ~340 cm -1

15 IR Spectra of Hydrated Clusters of Estradiol on A-ring trans-anti-(H 2 O) 3641 band C trans-anti -(H 2 O) trans-anti ν 3 (H 2 O) 3657 3641 3527 3746 ν 1 (H 2 O) trans-gauche(+) -(H 2 O) band D trans-gauche(+) ν 3 (H 2 O) 3657 3658 3527 3746 ν 1 (H 2 O) trans-gauche(+)-(H 2 O) UV wavenumber / cm -1 C D LIF A B Each conformer forms hydrogen bond on A-ring OH as proton donor. ν(D-ring) ν(A-ring) ν(D-ring) ν(A-ring)

16 Another Isomer of Hydrated Cluster of Estradiol a b c d gauche(+) type proton donor anti type proton acceptor B C D Different patterns of hydrogen bond are conceivable for D-ring OH

17 IR Spectra of Bare Estriol UV wavenumber / cm -1 IR wavenumber / cm -1 IR spectra in the region of OH stretching vibration IR spectra in the region of OH stretching vibration 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 estriol(E 3 ) 3723 3721 3538 3535 3722 3657 3656 3658 3663 3645 3644 3536 3655 3656 3657 3658 3664 3658 3644 A-ring OH cis region trans region IR wavenumber / cm -1 A-ring OH Band 1 - 6 Bare estriol Band 7 - 9 Hydrated cluster or its vibronic band A D cis- trans- LIF

18 Predicted Conformers of Bare cis-Estriol Conformational name Relative energy / cm -1 17 16 3c_16a_17a 810 3c_16g-_17a 208 3c_16g+_17a 740 3c_16a_17g+ 796 3c_16g-_17g+ 0.00 3c_16g+_17g+ 466 3c_16a_17g- 243 3c_16g+_17g- 46.3

19 Intramolecular hydrogen bond Intramolecular hydrogen bond 3c_16a_17a 810 3c_16g-_17a 208 3c_16g+_17a 740 3c_16a_17g+ 796 3c_16g-_17g+ 0.00 3c_16g+_17g+ 466 3c_16a_17g- 243 3c_16g+_17g- 46.3 Conformational name Relative energy / cm -1 Predicted Conformers of Bare cis-Estriol

20 IR Spectra of Bare cis-Estriol 3 2 1 IR wavenumber / cm -1 UV wavenumber / cm -1 1 2 3 estriol(E 3 ) 3c_16g-_17g+ 3c_16g-_17a 3c_16g+_17g- 3 17 16 3658 3662 3656 3657 3643 3645 Comparison of IR spectra of cis-estriol and results of frequency calculation Comparison of IR spectra of cis-estriol and results of frequency calculation 3c_16g-_17g+ 0.00 3c_16g+_17g- 46.3 3c_16g-_17a 208 Bare estriol Form the intramolecular hydrogen bond between16OH and 17OH LIF cis-

21 Summary estrone(E 1 )β-estradiol(E 2 )estriol(E 3 )  monomer Assign the conformation of bare estrogen. Estriol forms intramolecular hydrogen bond  1:1 hydrated cluster of estradiol On A-ring Each conformer forms hydrogen bond on A-ring OH. On D-ring Different pattern of hydrogen bond are conceivable.  Future work Hydrated clusters of estrone / estriol Methoxy estrogen

22 Thank you for kindly listening to my presentation and my poor English

23 Relative energy of bare estrone / cm -1

24 anti gauche(-) gauche(+) Relative energy of bare estradiol / cm -1

25 ≈ estradiol(A)-H 2 O estradiol(monomer) estradiol(D)-H 2 O Relative energy of clusters / cm -1

26 3c_16g-_17g+0.00 3c_16g+_17g-46.3 3c_16g-_17a208 3c_16a_17g-243 3c_16g+_17g+466 3c_16g+_17a740 3c_16a_17g+796 3c_16a_17a810 3t_16g-_17g+22.4 3t_16g+_17g-46.3 3t_16g-_17a207 3t_16a_17g-249 3t_16g+_17g+464 3t_16g+_17a730 3t_16a_17a796 3t_16a_17g+805 Relative energy of bare estriol Intramolecular hydrogen bond 16g-_17g+16g+_17g- 16g-_17a 16a_17g- 16g+_17g+16g+_17a 16a_17a 16a_17g+ / cm -1

27 IR Spectra of Bare Estrogen estradiol estrone estriol 7 1 2 3 8 9 4 5 6 1 2 a b c d IR wavenumber / cm -1 IR spectra in the region of OH stretching vibration

28 cis-anti trans-anti trans-gauche(+) cis-gauche(+) Predicted Conformers M05-2X / 6-311++G**

29 ~410 cm -1 ~260 cm -1 Barrier between each D-ring conformation of estradiol ~820 cm -1 Without ZPE correction

30 810 cm -1 cis trans Rotation of A-ring OH Without ZPE correction

31 π (HOMO) π* (LUMO) cis-anti trans-anti HOMO and LUMO of Estradiol

32 cis -anti trans -gauche(+) cis -gauche(+) trans -anti a b c d cis -anti trans -gauche(+) cis -gauche(+) trans -anti Assignment of A-ring OH conformations

33 estradiol(D)-H 2 O Estradiol(D)-H 2 O cis-anti trans-gauche(+) cis-gauche(+) trans-anti cis-anti trans-gauche(+) cis-gauche(+) trans-anti gauche(+) type proton donor anti type proton acceptor red shift blue shift

34 1-cis-naphthol 1-trans-naphthol 2-trans-naphthol 2-cis-naphthol M05-2X / 6-311++G** TD-DFT calculation

35 TD-DFT Calculation for conformers of bare estriol UV wavenumber / cm -1 trans- 16g+_17g-16g+_17a16g+_17g+16a_17g-16a_17a16g-_17a16a_17g+16g_17g+ Position / cm -1 3514035141351443514635149351503515335155 Relative energy / cm -1 4673046424979620780522 2 1 3 5 4 6 cis- 16g+_17g-16g+_17a16g+_17g+16a_17g-16a_17a16g-_17a16a_17g+16g_17g+ Position / cm -1 3505135054350573505835061 3506535067 Relative energy / cm -1 467404662438102080796 cis- trans-

36 Lifetime Time / ns Monomer Cluster τ = 5 ns τ = 15 ns

37 Predicted Conformers of Bare trans-Estriol Conformational name Relative energy / cm -1 3 17 16 3t_16a_17a 796 3t_16g-_17a 207 3t_16g+_17a 730 3t_16a_17g+ 805 3t_16g-_17g+ 22.4 3t_16g+_17g+ 464 3t_16a_17g- 249 3t_16g+_17g- 46.3

38 Predicted Conformers of Bare trans-Estriol 3t_16a_17a 796 3t_16g-_17a 207 3t_16g+_17a 730 3t_16a_17g+ 805 3t_16g-_17g+ 22.4 3t_16g+_17g+ 464 3t_16a_17g- 249 3t_16g+_17g- 46.3 Conformational name Relative energy / cm -1

39 IR wavenumber / cm -1 7 1 2 3 8 9 4 5 6 IR spectra of Bare Estriol 16g-_17g+ 16g+_17g- 16g-_17a 16a_17g- 16g+_17g+ 16g+_17a 16a_17a 16a_17g+ 16g-_17g+ 16g+_17g- 16g-_17a 16a_17g- 16g+_17g+ 16g+_17a 16a_17a 16a_17g+ cis region trans region Intramolecularhydrogen bond

40 Relative Energy of Monohydrated Estriol Isomers 3t_16g+_17g-_(A)-H 2 O3t_16g+_17g-_(D)-H 2 O 0.00 cm -1 ~1,000 cm -1 More stable

41 Relative Energy of Monohydrated Estradiol Isomers cis-gauche(+)-(A)-H 2 O cis-gauche(+)-(D)-H 2 O cis-anti-(D)-H 2 O 0.00 cm -1 ~330 cm -1 ~460 cm -1 More stable cis-anti-(A)-H 2 O 62.9cm -1

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