Elsevier

Chemical Physics

Volume 515, 14 November 2018, Pages 381-386
Chemical Physics

Laser spectroscopic study on sinapic acid and its hydrated complex in a cold gas phase molecular beam

https://doi.org/10.1016/j.chemphys.2018.07.007Get rights and content

Abstract

The S1 (ππ)-S0 electronic spectrum and the infrared spectrum in the OH stretching region of sinapic acid (SA) and its 1:1 complex with water (SA-H2O) are observed in a supersonically cooled molecular beam. Supersonically-cooled SA and SA-H2O complex are obtained by a combination of laser ablation with a newly developed pulsed channel nozzle. Both SA and SA-H2O exhibit sharp electronic spectra, and measurements of UV-UV hole-burning spectra and time-dependent density functional theory (TD-DFT) calculation indicate that the observed vibronic bands belong to two conformers, syn and anti, in both SA and the SA-H2O complex. The OH stretching vibrations are observed with IR-UV double resonance spectroscopy. A comparison of the observed IR spectrum and the DFT-calculated one indicates that SA-H2O has the structure in which a carboxylic (COOH) group and the water form a cyclic hydrogen (H)-bond. The OH stretch of COOH is red-shifted as large as 600 cm−1 in the complex. The S1 lifetime of SA at the zero-point energy level is obtained to be 1.9 ns. This S1 lifetime is shorter than the reported one of its ester derivative (methyl sinapate, MS (Dean et al., J. Am. Chem. Soc. 136 (2014) 1478–14795)) but is much longer than the para-substituted cinnamates, p-hydroxy methylcinnamate (p-HMC (Shimada et al., Phys. Chem. Chem. Phys. 14 (2012) 8999–9005)) and p-methoxy methylcinnamate (p-MMC (Miyazaki et al., J. Chem. Phys. 141 (2014) 244313)). A calculation at TD-DFT level indicates that this long lifetime of SA is due to that the 1 state and the transition states along the trans → cis isomerization in S1 (ππ) are located much higher in energy than p-HMC and p-MMC. This may lead a main nonradiative channel of SA in the low energy region to be the multistep intersystem crossing to T1 (3ππ) via the 3 state.

Introduction

Sinapic acid (SA), shown in Scheme 1, is one of the hydroxyl cinnamic acids. This molecule is known as an effective MALDI (matrix assisted laser desorption ionization) matrix [1], [2] for protein mass spectroscopy, because it has a large absorption cross section in the UV region and releases a proton. In nature, SA and feluric acid (FA, Scheme 1) exist in the cell wall as cell-wall polymers. The polymers are formed through cross-linking by photochemical reaction or radical coupling reactions [3], [4], [5], [6]. In addition to the role of building blocks of polymer in the cell wall, many attentions are also paid to the photochemical behavior of the derivative of cinnamic acids experimentally [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23] and theoretically [9], [24], [25], [26], [27], [28], [29], [30]. In the electronic ground state (S0), cinnamic acids have the trans (E) conformation along the propenyl double bond. Upon the UV-B irradiation in the 280–315 nm region, the molecules are excited to the S1 (ππ) state and return back to either trans (E) or cis (Z) isomer [7], [8], [9], [10], [11], [12], [20]. The relaxation processes are very effective so that almost all the absorbed UV energy is translated finally to thermal energy. Because of this property, cinnamic acids are thought as good candidates for commercial sunscreen reagents [31], [32]. The photochemistry of cinnamic acids and their derivatives in the gas phase has been extensively studied by several groups [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23]. Buma and coworkers reported the S1-S0 electronic spectra of several para-substituted cinnamates [12], [13], [14], [15]. They found that after the photoexcitation to S1 (ππ), the molecule relaxes very rapidly to some transient states having a lifetime of ∼30 ns. They suggested that the transient state is probably the 1 state. Zwier and coworkers studied the S1(ππ)-S0 electronic spectra of jet-cooled SA, sinapoyl malate (SM) and their ester derivatives [16]. They reported that SM shows a broad structureless absorption spectrum among the species having similar complexity of the structure even under jet-cooled condition. They tentatively described the broadening of the UV spectrum to the coupling between the S1 and 1 states. Stavros and coworkers measured the S1-S0 electronic spectrum and excited state lifetime of ethyl ferulate (EF) by ultrafast pump-probe spectroscopy [17]. From the time profile, they proposed a stepwise decay involving S2 (nπ) and T1 (3ππ) states as the possible decay process. Stavros and coworkers also carried out ultrafast pump-probe spectroscopy for SA and sinapoyl malate (SM) in solution [18]. They observed the transient S1 → Sn absorption spectra after exciting SA at ∼320 nm (∼31300 cm−1). The transient absorption showed multi-exponential decay described by three time constants. The three constants were attributed to the stepwise processes involving vibrational relaxation (τ1 = ∼100 fs) within S1 (1ππ), internal conversion (IC) to the 21ππ state via S1/21ππ conical intersection (CI) (τ2 = ∼1 ps), and IC to S03 = 12–22 ps), which is followed by isomerization. Ebata and coworkers also have been studying the nonradiative decay (NRD) route of the derivatives of methylcinnamate (MC) in the gas phase [19], [20], [21], [22], [23]. Very recently, they reported the NRD leading to the isomerization of para-methoxy methylcinnamate (p-MMC) [22] and para-hydroxy methylcinnamate (p-HMC) [23] occurs via [trans-S1 → 1 → T1 → cis-S0] stepwise scheme, while in ortho- and meta-hydroxy methylcinnamate (o-, m-HMC), the isomerization occurs via [trans-S1 → twisting along the C = C double bond to 90° on S1 → cis-S0] scheme [23].

Though the NRD process of bare cinnamic acids and cinnamates has been extensively studied so far, little is known about the effect of hydration. Most of NRD initiated from the UV excitation to the S1 (ππ) state involves the internal conversion (IC) to 1 excited state via conical intersection (CI), and this state is strongly affected by the environment such as hydrogen (H)-bonding. For example, Ebata et al. reported that H-bonding of a water to the OH group of p-HMC elongates the S1 lifetime by two orders of magnitudes [19], while the H-bonding of the water to the carbonyl oxygen of p-MMC shortens the S1 lifetime, suggesting the above two NRD channels are competing in these molecules [20].

In the present study, we report the electronic and vibrational spectra of SA and its complex with water under the cold gas phase condition. Since cinnamic acids and their derivatives are nonvolatile, either thermal heating or laser ablation is necessary to vaporize and introduce in a supersonic beam. However, upon heating cinnamic acids easily decompose by thermal decarboxylation [33]. Zwier and coworkers successfully measured the S1-S0 electronic spectrum of jet-cooled SA by using laser ablation technique [16]. However, none of the electronic spectrum of the hydrated complex of SA has been reported. It is of great interest to investigate the hydrated structure of SA and the effect of the hydration on its photochemical process including trans-cis isomerization. In the present study we measure the UV spectra of SA and SA-H2O 1:1 complex by resonance enhanced two-photon ionization (R2PI) and the infrared spectra by IR-UV double resonance (DR) spectroscopy. By using a newly developed laser ablation combined with a channel nozzle supersonic beam setup, well resolved R2PI spectra of SA and SA-H2O complex were obtained. The structures of SA and SA-H2O 1:1 are discussed by the comparison of the observed UV and IR spectra with those of calculated ones at DFT level. The S1 lifetime of SA is also measured by picosecond pump-probe spectroscopy, and the obtained lifetime is compared with those of other cinnamate derivatives.

Section snippets

Experimental and computational

Fig. 1 shows a schematic experimental setup. The mixture of solid powder of SA and carbon black is put on the side of a graphite disk with a diameter of 80 mm. The disk is attached at the side of a channel nozzle and is rotated by a stepping motor. The channel nozzle is beak-shaped and an ablation laser beam (1.064 μm) passes through the slit of the channel nozzle and irradiates the sample powder on the graphite disk to vaporize. The pulsed Ar carrier gas at a backing pressure of 15 atm is

S1-S0. electronic spectra

Fig. 2(a) and (b) show the LIF and R2PI spectrum of the S1-S0 transition of jet-cooled SA. The R2PI spectrum of SA is previously reported by Zwier and coworkers [16], and the present spectrum is essentially the same with their spectrum. On the other hand, to the best of our knowledge, the LIF detection is the first report of the jet-cooled spectrum by combining laser ablation method. The signal-to-noise ratio of the LIF spectrum as good as R2PI detection. According to the study of Zwier and

Acknowledgements

T. E. acknowledges the financial support from the Institute for Quantum Chemical Exploration. K. Y. is grateful for the financial supports from Building of Consortia for the Development of Human Resources in Science and Technology, MEXT. This work was partly supported by the JSPS KAKENHI Grant Number JP16H04098 (Y. I.). Part of the calculations in this paper was carried out by using a supercomputer at Okazaki Research Facilities (Research Center for Computational Science).

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