Because of its fundamental importance in many branches of science, hydrogen bonding is a subject of intense contemporary research interest. The physical and chemical properties of hydrogen bonds in the ground state have been widely studied both experimentally and theoretically by chemists, physicists, and biologists. However, hydrogen bonding in the electronic excited state, which plays an important role in many photophysical processes and photochemical reactions, has scarcely been investigated. Upon electronic excitation of hydrogen-bonded systems by light, the hydrogen donor and acceptor molecules must reorganize in the electronic excited state because of the significant charge distribution difference between the different electronic states. The electronic excited-state hydrogen-bonding dynamics, which are predominantly determined by the vibrational motions of the hydrogen donor and acceptor groups, generally occur on ultrafast time scales of hundreds of femtoseconds. As a result, state-of-the-art femtosecond time-resolved vibrational spectroscopy is used to directly monitor the ultrafast dynamical behavior of hydrogen bonds in the electronic excited state. It is important to note that the excited-state hydrogen-bonding dynamics are coupled to the electronic excitation. Fortunately, the combination of femtosecond time-resolved spectroscopy and accurate quantum chemistry calculations of excited states resolves this issue in laser experiments. Through a comparison of the hydrogen-bonded complex to the separated hydrogen donor or acceptor in ground and electronic excited states, the excited-state hydrogen-bonding structure and dynamics have been obtained. Moreover, we have also demonstrated the importance of hydrogen bonding in many photophysical processes and photochemical reactions. In this Account, we review our recent advances in electronic excited-state hydrogen-bonding dynamics and the significant role of electronic excited-state hydrogen bonding on internal conversion (IC), electronic spectral shifts (ESS), photoinduced electron transfer (PET), fluorescence quenching (FQ), intramolecular charge transfer (ICT), and metal-to-ligand charge transfer (MLCT). The combination of various spectroscopic experiments with theoretical calculations has led to tremendous progress in excited-state hydrogen-bonding research. We first demonstrated that the intermolecular hydrogen bond in the electronic excited state is greatly strengthened for coumarin chromophores and weakened for thiocarbonyl chromophores. We have also clarified that the intermolecular hydrogen-bond strengthening and weakening correspond to red-shifts and blue-shifts, respectively, in the electronic spectra. Moreover, radiationless deactivations (via IC, PET, ICT, MLCT, and so on) can be dramatically influenced through the regulation of electronic states by hydrogen-bonding interactions. Consequently, the fluorescence of chromophores in hydrogen-bonded surroundings is quenched or enhanced by hydrogen bonds. Our research expands our understanding of the n...

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To study the early time hydrogen-bonding dynamics of chromophore in hydrogen-donating solvents upon photoexcitation, the infrared spectra of the hydrogen-bonded solute-solvent complexes in electronically excited states have been calculated using the time-dependent density functional theory (TDDFT) method. The hydrogen-bonding dynamics in electronically excited states can be widely monitored by the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds. In this study, we have demonstrated that the intermolecular hydrogen bonds between coumarin 102 (C102) and hydrogen-donating solvents are strengthened in the early time of photoexcitation to the electronically excited state by theoretically monitoring the stretching modes of C=O and H-O groups. This is significantly contrasted with the ultrafast hydrogen bond cleavage taking place within a 200-fs time scale upon electronic excitation, proposed in many femtosecond time-resolved vibrational spectroscopy experiments. The transient hydrogen bond strengthening behaviors in excited states of chromophores in hydrogen-donating solvents, which we have demonstrated here for the first time, may take place widely in many other systems in solution and are very important to explain the fluorescence-quenching phenomena associated with some radiationless deactivation processes, for example, the ultrafast solute-solvent intermolecular electron transfer and the internal conversion process from the fluorescent state to the ground state.

Solute-solvent intermolecular photoinduced electron transfer (ET) reaction was proposed to account for the drastic fluorescence quenching behaviors of oxazine 750 (OX750) chromophore in protic alcoholic solvents. According to our theoretical calculations for the hydrogen-bonded OX750-(alcohol)(n) complexes using the time-dependent density functional theory (TDDFT) method, we demonstrated that the ET reaction takes place from the alcoholic solvents to the chromophore and the intermolecular ET passing through the site-specific intermolecular hydrogen bonds exhibits an unambiguous site selectivity. In our motivated experiments of femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD), it could be noted that the ultrafast ET reaction takes place as fast as 200 fs. This ultrafast intermolecular photoinduced ET is much faster than the diffusive solvation process, and even significantly faster than the intramolecular vibrational redistribution (IVR) process of the OX750 chromophore. Therefore, the ultrafast intermolecular ET should be coupled with the hydrogen-bonding dynamics occurring in the sub-picosecond time domain. We theoretically demonstrated for the first time that the selected hydrogen bonds are transiently strengthened in the excited states for facilitating the ultrafast solute-solvent intermolecular ET reaction.

The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state hydrogen-bonding dynamics of fluorenone (FN) in hydrogen donating methanol (MeOH) solvent. The infrared spectra of the hydrogen-bonded FN-MeOH complex in both the ground state and the electronically excited states are calculated using the TDDFT method, since the ultrafast hydrogen-bonding dynamics can be investigated by monitoring the vibrational absorption spectra of some hydrogen-bonded groups in different electronic states. We demonstrated that the intermolecular hydrogen bond C=O...H-O between fluorenone and methanol molecules is significantly strengthened in the electronically excited-state upon photoexcitation of the hydrogen-bonded FM-MeOH complex. The hydrogen bond strengthening in electronically excited states can be used to explain well all the spectral features of fluorenone chromophore in alcoholic solvents. Furthermore, the radiationless deactivation via internal conversion (IC) can be facilitated by the hydrogen bond strengthening in the excited state. At the same time, quantum yields of the excited-state deactivation via fluorescence are correspondingly decreased. Therefore, the total fluorescence of fluorenone in polar protic solvents can be drastically quenched by hydrogen bonding.

We study the process e + e − → π + π − J/ψ at a center-of-mass energy of 4.260 GeV using a 525 pb −1 data sample collected with the BESIII detector operating at the Beijing Electron Positron Collider. The Born cross section is measured to be (62.9 ± 1.9 ± 3.7) pb, consistent with the production of the Y (4260). We observe a structure at around 3.9 GeV/c 2 in the π ± J/ψ mass spectrum, which we refer to as the Zc(3900). If interpreted as a new particle, it is unusual in that it carries an electric charge and couples to charmonium. A fit to the π ± J/ψ invariant mass spectrum, neglecting interference, results in a mass of (3899.0 ± 3.6 ± 4.9) MeV/c 2 and a width 3 of (46 ± 10 ± 20) MeV. Its production ratio is measured to be R = σ(e + e − →π ± Zc(3900) ∓ →π + π − J/ψ)) σ(e + e − →π + π − J/ψ) = (21.5 ± 3.3 ± 7.5)%. In all measurements the first errors are statistical and the second are systematic. PACS numbers: 14.40.Rt, 14.40.Pq, 13.66.Bc Since its discovery in the initial-state-radiation (ISR) process e + e − → γ ISR π + π − J/ψ [1], and despite its subsequent observations [2][3][4][5], the nature of the Y (4260) state has remained a mystery. Unlike other charmonium states with the same quantum numbers and in the same mass region, such as the ψ (4040) A similar situation has recently become apparent in the bottomonium system above the BB threshold, where there are indications of anomalously large couplings between the Υ(5S) state (or perhaps an unconventional bottomonium state with similar mass, the Y b (10890)) and the π + π − Υ(1S, 2S, 3S) and π + π − h b (1P, 2P ) final states [14,15]. More surprisingly, substructure in these π + π − Υ(1S, 2S, 3S) and π + π − h b (1P, 2P ) decays indicates the possible existence of charged bottomoniumlike states [16], which must have at least four constituent quarks to have a non-zero electric charge, rather than the two in a conventional meson. By analogy, this suggests there may exist interesting substructure in the Y (4260) → π + π − J/ψ process in the charmonium region.In this Letter, we present a study of the process e + e − → π + π − J/ψ at a center-of-mass (CM) energy of √ s = (4.260± 0.001) GeV, which corresponds to the peak of the Y (4260) cross section. We observe a charged structure in the π ± J/ψ invariant mass spectrum, which we refer to as the Z c (3900). The analysis is performed with a 525 pb −1 data sample collected with the BESIII detector, which is described in detail in Ref. [17]. In the studies presented here, we rely only on charged particle tracking in the main drift chamber (MDC) and energy deposition in the electromagnetic calorimeter (EMC).The GEANT4-based Monte Carlo (MC) simulation software, which includes the geometric description of the BE-SIII detector and the detector response, is used to optimize the event selection criteria, determine the detection efficiency, and estimate backgrounds. For the signal process, we use a sample of e + e − → π + π − J/ψ MC events generated assuming the π + π − J/ψ is produced via Y (4260) decays, and using the...

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ABSTRACT:We have developed a near-IR reversible fluorescent probe containing an organoselenium functional group that can be used for the highly sensitive and selective monitoring of peroxynitrite oxidation and reduction events under physiological conditions. The probe effectively avoids the influence of autofluorescence in biological systems and gave positive results when tested in both aqueous solution and living cells. Real-time images of cellular peroxynitrite were successfully acquired. P eroxynitrite (ONOO À ) performs as a strong oxidizing agent in physiological and pathological processes. 1À3 In vivo, abnormally high concentrations of ONOO À are formed from the fast reaction between nitric oxide (NO) and superoxide anion (O 2 À ), which requires no enzymatic catalysis. 4 The peroxynitrite anion is relatively stable, but the acid form (ONOOH) rapidly decays to nitrate. Although the half-life of ONOOH is ∼1 s at pH 7.40, 5 the oxidative species contributes to signal transduction, homeostasis regulation, and oxidative damage, which forms a unique biological oxidationÀreduction cycle indicating human health and disease.6 Therefore, the development of reversible detection technology for peroxynitrite would have important biomedical significance. In comparison with other technologies, fluorescence microscopy provides greater sensitivity, less invasiveness, and more convenience.7 Especially the use of near-IR (NIR) light (650À900 nm) allows deep penetration into tissues and efficaciously avoids the influence of bioautofluorescence. However, there exists a major obstacle to the design of novel fluorescent probes for ONOO À , namely, the nitro group, which is considered to be a strong quencher for fluorophores.3 To date, only a few fluorescent probes for ONOO À detection have been reported. 8 Thus, we anticipate widespread interest in a redoxreversible NIR fluorescent probe, which would exhibit much more value for visualizing cycles of redox signaling and stress caused by peroxynitrite.9 Here we report a redox-responsive NIR fluorescent probe for continuous monitoring of ONOO À . ONOO À is modulated by cellular antioxidant defense systems, 1,10 in which selenium (Se) plays an important role as the active site of the antioxidant enzyme glutathione peroxidase (GPx).11 GPx can catalyze the reduction of ONOO À by glutathione (GSH) via a unique ping-pong mechanism.12 Taking the advantage of this, we mimicked the catalytic cycle and developed an NIR fluorescent probe containing an organoselenium moiety that can be used for reversible peroxynitrite detection.As an overall strategy, cyanine (Cy), an NIR fluorescent dye with a high extinction coefficient, 13 was selected as a signal transducer, while 4-(phenylselenyl)aniline (PSe) was selected as a modulator because it can respond sensitively to ONOO À . 11,14Following the ping-pong mechanism, 12 we designed and synthesized a new NIR reversible fluorescent probe (Cy-PSe) for detection of ONOO À in living cells through a fast photoinduced electron transfer (PET) process. ...