IN THE GAS PHASE AND IN SOLUTION DNA SUGARS: IN THE GAS PHASE AND IN SOLUTION Iciar Uriarte Spectroscopy Group, Universidad del País Vasco Bilbao, Spain ISMS, Champaign-Urbana, Illinois, June 2017

Sugars in DNA/RNA Sugars DNA Sugar DEOXYRIBOSE RNA Sugar RIBOSE

D-ribose α Pyranose β Open chain α Furanose β 4C1 1C4 Ribose 4C1 1C4 3T4 1T2

RNA DNA Ribopyranoside Chemical synthesis Deoxyribopyranoside Ribose Ribopyranoside Angew. Chem. Int. Ed. 51, 3119-3124, 2012 Chemical synthesis Deoxyribopyranoside Angew. Chem. Int. Ed. 52, 11840-11845, 2013 RNA Chemical synthesis DNA Methyl β-D-ribofuranoside Chem. Commun. 52, 6241-6244, 2016 Methyl deoxyribofuranoside

Arbitrary Wave Generator Methodology CP-FTMW Arbitrary Wave Generator Chamber Scope Amplifier Resolution: ~ 10 kHz | Broadband (7-18 GHz)

CP-FTMW 3 valves Chamber Methodology Resolution: ~ 10 kHz | Broadband (7-18 GHz)

Ultrafast laser vaporization Methodology FTMW Ultrafast laser vaporization Resolution: ~ 3 kHz | Bandwidth ~ 1MHz

Vaporization method Syrup Powder Methodology Vaporization method Heating Ultrafast laser Syrup Powder

Alpha Rotational spectrum 13C in natural abundance ~ 20M cycles

Alpha GG GA1 GA2 Same ring puckering (~ 2T1) 0.0 kJ/mol 2.6 kJ/mol ∆(E+ZPE) at B3LYP-D3/6-311++G(d,p)

Beta Rotational spectrum 13C in natural abundance ~ 40M cycles

Beta 4E E2-1T2 GG GA1 GA2 Change in ring puckering 0.0 kJ/mol ∆(E+ZPE) at B3LYP-D3/6-311++G(d,p)

Cremer-Pople diagram Ring puckering α β

Aqueous solution β NMR spectroscopy Combination of: Molecular Dynamics NMR (aqueous media) NMR spectroscopy Molecular Dynamics Combination of: 2.8% 4.3% 6.6% 6.8% 4.1% 2.1% 1.4% 1.6% 1.5% 1.7% 1.9% 3.4% 7.9% 15.3% 14.6% 9.6% 5.6% 3.8% 2.7% 2.4% β

Aqueous solution β 9.6% 14.6% 15.3% NMR (aqueous media) 2.8% 2.4% 4.3% 2.7% β 6.6% 3.8% 6.8% 5.6% 4.1% 9.6% 2.1% 14.6% 1.4% 15.3% 1.6% 7.9% 1.5% 3.4% 1.7% 1.9%

Francisco José Basterretxea Acknowledgements MW Group (UPV/EHU) Montse Vallejo López Camilla Calabrese Francisco José Basterretxea Emilio J. Cocinero Spectroscopy Group (UPV-EHU) Collaborators Alberto Lesarri Sonia Melandri Zbigniew Kisiel Walther Caminati Jens-Uwe Grabow Brooks H. Pate Francisco Corzana Benjamin G. Davis

The 25th International Conference on High Resolution Molecular Spectroscopy September 3rd-7th, 2018 Bilbao, Spain Chairmen: Alberto Lesarri and Emilio J. Cocinero