1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 z Electro, Physical & Theoretical Chemistry H 2 O 2 and HO À Solvation Dynamics: Solute Capabilities and Solute-Solvent Molecular Interactions Jiasheng S. Chen, [a, b] Chuang Yao,* [b] Xinjuan J. Liu, [c] Xi Zhang, [d] Chang Q. Sun, [e] and Yongli L. Huang* [a] We show spectrometrically that H 2 O 2 and HO À solvation resolves the H À O stretching vibration from the mode of the ordinary water centered at ~ 3200 cm À1 to its below by O:b:O compression. An excessive mode due H 2 O 2 solute appears at ~ 3550 cm À1 and due HO À at ~ 3610 cm À1 , which features the effect of molecular solute bond-order deficiency. The O:b:O compression has the same effect to applied pressure that elongates the solvent H À O bond and shortens the O:H nonbond. The H 2 O 2 is less than the HO À capable of raising the surface stress and transforming the fraction of the H À O bonds because of the involvement of solute-solute interactions. Introduction Solvation of hydrogen peroxide (H 2 O 2 ) and hydroxide (HO À ) in basic solutions forms important ingredients for the bio- and organic-chemistry such as cell functioning, signal processing, regulating, etc. [1–4] However, fine resolution and clarification of the solute-solvent molecular interactions and the solute capabilities of transforming the solution surface stress and the hydrogen bonding network remain yet great challenge. For instance, H 2 O 2 , being less stable and easily explosive, is becoming increasingly fashionable as an oxidant both in industry sectors and in academia due to environmental catalytic, [5] health care, [6,7] medication, [8] electrochemical sens- ing, [9] light-sensing, [10] oxidant stressing, [11] cell delivery, [12] cancer therapy, [13,14] etc. Overwhelming contributions have been made with foci mainly on production and application of the H 2 O 2 solutions in various fields. [15,16] For instances, H 2 O 2 solutions are widely used for bleaching in hospitals and factories. H 2 O 2 can bleach the textile waste water by using in-situ production of hydrogen peroxide/hydroxyl radicals. [17] As an oxidant, H 2 O 2 provides electrons in fuel cells. [18] In the case of plants dealing with drought, H 2 O 2 plays a key role in the process of inducing stomatal closure to defend cells to cope with drought. [19] H 2 O 2 is also presented in plants as a signaling molecule. [20] The presence of H 2 O 2 in the somatic cells of animals is beneficial to organisms. In the heart regeneration process, fluorescence signal shows that H 2 O 2 injures the Duox and Nox2 to produce H 2 O 2 , approaching the highest concentration of 30 mMol, distributed in the heart membrane and adjacent myocardium, as the active oxygen signal by degradation of redox-sensitive phosphatase Dusp6, lifting the inhibition of MAPK signaling pathways and enhance pERK, thereby promoting myocardial proliferation, regeneration and inhibition of cardiac fibrosis. [21] However, little has been known about the H 2 O 2 and HO À capabilities to functionalize their aqueous solutions from the bond-relaxation and polarization points of view. In this communication, we report our examination of the solvation dynamics and the capabilities of H 2 O 2 and HO À to transform the surface stress, solute H À O bonds, and solvent hydrogen bond (O:H À O or HB with “:” being the lone pair of electrons). The solute capability examination is conducted with compar- ison of the H 2 O 2 , the HO À in KOH solution [2] and the effect of mechanical compression of water [22] on the O:H À O bond segmental vibration frequencies. We used the Raman differ- ential phonon spectrometrics (DPS) [23] and the contact angle detection. Uncovering the H À O vibration mode signatures of both the solvent O:H À O bond and the solute H À O bonds, the DPS confirms the essentialities not only of the O:b:O super-HB compressor [2] associated with the excessive number of electron lone pairs in solution but also the effect of bond-order- deficiency on the solute H À O bond contraction. [24] [a] J. S. Chen, Dr. Y. L. Huang Key Laboratory of Low-dimensional Materials and Application Technology (Ministry of Education) School of Materials Science and Engineering Xiangtan University Xiangtan – 411105, China E-mail: huangyongli@xtu.edu.cn [b] J. S. Chen, Dr. C. Yao Key Laboratory of Extraordinary Bond Engineering and Advanced Mate- rials Technology (EBEAM) Yangtze Normal University Chongqing - 408100, China E-mail: yaochuang@yznu.cn [c] Dr. X. J. Liu Institute for Coordination Bond Engineering China Jiliang University Hangzhou - 310018, China [d] Dr. X. Zhang Institute of Nanosurface Science and Engineering Shenzhen University Shenzhen - 518060, China [e] Prof. C. Q. Sun NOVITAS, School of EEE Nanyang Technological University Singapore - 639798 Full Papers DOI: 10.1002/slct.201701334 8517 ChemistrySelect 2017, 2, 8517 – 8523  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim