Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization

Bilirubin is a neurotoxic product responsible for neonatal jaundice, which is generally treated by phototherapy. The photoreaction involves ultrafast internal conversion via an elusive intermediate and Z–E isomerization with minor yield (less than 3% in solution). The structure of the intermediate remains unclear. Here, the combination of UV-vis and mid-IR ultrafast transient absorption spectroscopy reports a comprehensive picture of the mechanism and provides essential structural information about the intermediate species. Thus, spectral dynamics during the earliest ps unveils a wavepacket travelling from the Franck–Condon region to the crossing point with a dark state. The latter shows a tighter molecular skeleton than the ground state and decays with 15 ps time constant. Remarkably, the relative contribution of a non-decaying component increases linearly with pump energy, suggesting that Z–E isomerization could also be triggered by two-photon excitation. Implications for the photochemistry of protein-bound open tetrapyrroles are discussedJLPL thanks the Spanish Ministry of Science and Innovation (MICINN) for funding through the grant CTQ2010-17026 (FEDER Funds) and the ‘‘Ramón y Cajal’’ Program 2009, as well as the Xunta de Galicia (Spain) for grants EM2012/091, GPC2013/052 and R2014/051. CCB thanks the Spanish Ministry of Education for a FPU doctoral grantS

Excited-State Proton and Charge Transfer in Protonated Amino and Methylated Derivatives of 2-(2′-Hydroxyphenyl)benzimidazole

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry B 2015, 119, 2475–2489, DOI: 10.1021/jp507917u, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jp507917u. This article may be used for non-commercial purposes onlyWe studied the excited-state behavior of a family of mono- and diprotonated derivatives of 2-phenylbenzimidazole in different solvents, using steady-state and time-resolved fluorescence spectroscopy. The species investigated were 2-(4′-amino-2′-hydroxyphenyl)benzimidazole (1), the diethylamino analogue 2-(4′-N,N-diethylamino-2′-hydroxyphenyl)benzimidazole (2) and its N-methylated derivative 1-methyl-2-(4′-N,N-diethylamino-2′-hydroxyphenyl)benzimidazole (3). The O-methoxy derivatives of 2 and 3 (2-OMe and 3-OMe), and the simpler models 2-phenylbenzimidazole (4) and its 4′-amino (5) and 4′-dimethylamino (6) derivatives were also studied. We found that the dications of 1, 2, and 3 (protonated at the benzimidazole N3 and at the amino group) were strong photoacids, which were deprotonated at the hydroxyl group upon excitation in aqueous solution (totally for 2 and 3) to give a tautomer of the ground-state monocation. In contrast, no photodissociation was observed for the monocations of these species. Instead, some of the monocations studied behaved as molecular rotors, for which electronic excitation led to a twisted intramolecular charge transfer (TICT) state. The monocations of 2, 3, 2-OMe, 3-OMe, and 6, protonated at the benzimidazole N3, experienced a polarity- and viscosity-dependent radiationless deactivation associated with a large-amplitude rotational motion. We propose that this process is connected to an intramolecular charge transfer from the dimethylaminophenyl or diethylaminophenyl moiety (donor) to the protonated benzimidazole group (acceptor) of the excited monocation, which yields a twisted charge-transfer species. No fluorescence from this species was detected except for 3 and 3-OMe in low-viscosity solventsWe are indebted to the European Regional Development Fund, the Spanish Ministry of Economy and Competitiveness (Grant CTQ2010-17835), and the Xunta de Galicia (Grants GPC2013/052, CN2012/314, and EM2012/091) for financial support of our work. S.R. and J.L.P.L. are thankful for a MEC-FPU fellowship and a “Ramón y Cajal” contract, respectivelyS

Femtosecond pump/supercontinuum-probe spectroscopy: Optimized setup and signal analysis for single-shot spectral referencing

A setup for pump/supercontinuum-probe spectroscopy is described which (i) is optimized to cancel fluctuations of the probe light by single-shot referencing, and (ii) extends the probe range into the near-uv (1000–270 nm). Reflective optics allow 50 μm spot size in the sample and upon entry into two separate spectrographs. The correlation γsame between sample and reference readings of probe light level at every pixel exceeds 0.99, compared to γconsec<0.92 reported for consecutive referencing. Statistical analysis provides the confidence interval of the induced optical density, ΔOD. For demonstration we first examine a dye (Hoechst 33258) bound in the minor groove of double-stranded DNA. A weak 1.1 ps spectral oscillation in the fluorescence region, assigned to DNA breathing, is shown to be significant. A second example concerns the weak vibrational structure around t=0 which reflects stimulated Raman processes. With 1% fluctuations of probe power, baseline noise for a transient absorption spectrum becomes 25 μOD rms in 1 s at 1 kHz, allowing to record resonance Raman spectra of flavine adenine dinucleotide in the S0 and S1 stateWe are grateful to the Deutsche Forschungsgemeinschaft for support (SFB 450 and Cluster of Excellence “Unifying Concepts in Catalysis”)S

Photoinduced Proton and Charge Transfer in 2‑(2′- Hydroxyphenyl)imidazo[4,5‑b]pyridine

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry B 2013, 117, 884–896, DOI: 10.1021/jp311709c, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jp311709c. This article may be used for non-commercial purposes onlyThis paper deals with the interplay between solvent properties and isomerism of 2-(2′-hydroxyphenyl)imidazo[4,5-b]pyridine (1), and the proton and charge-transfer processes that the different isomers undergo in the first-excited singlet state. We demonstrate the strong influence of these processes on the fluorescence properties of 1. We studied the behavior of 1 in several neutral and acidified solvents, by UV–vis absorption spectroscopy and by steady-state and time-resolved fluorescence spectroscopy. The fluorescence of 1 showed a strong sensitivity to the environment. This behavior is the result of conformational and isomeric equilibria and the completely different excited-state behavior of the isomers. For both neutral and cationic 1, isomers with intramolecular hydrogen bond between the hydroxyl group and the benzimidazole N undergo an ultrafast excited-state intramolecular proton transfer (ESIPT), yielding tautomeric species with very large Stokes shift. For both neutral and cationic 1, isomers with the OH group hydrogen-bonded to the solvent behave as strong photoacids, dissociating in the excited state in solvents with basic character. The pyridine nitrogen exhibits photobase character, protonating in the excited state even in some neutral solvents. An efficient radiationless deactivation channel of several species was detected, which we attributed to a twisted intramolecular charge-transfer (TICT) process, facilitated by deprotonation of the hydroxyl group and protonation of the pyridine nitrogenThis work has been supported by the Spanish Government and the European Regional Development Fund (Grant CTQ2010-17835) and the Xunta de Galicia (Grant CN 2012/314). A.B., M.V., and J.L.P.L. are thankful for a “Fundación Segundo Gil Dávila” fellowship, a MEC-FPU fellowship, and a “Ramon y Cajal” contract, respectivelyS

Synthesis and Characterization of a New Triptycene-Based Tripod

The 18th International Electronic Conference on Synthetic Organic Chemistry session General Organic SynthesisHerein, we report an efficient and facile synthesis of a new triptycene based tripodal ligand containing both imine functionality and phenolic pendant arms. This tripodal unit is a potential building block for constructing novel supramolecular architectures. The newly synthesized 2,6,14-triaminotriptycene derivative, which was characterized by FT-IR, UV−Vis absorption, mass and NMR spectroscopic techniques has interesting properties such as high solubility in common organic solvents and fluorescence emission in THF solution (λ = 550 nm

Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry Letters 2014, 5, 989–994, DOI: 10.1021/jz5001648, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jz5001648. This article may be used for non-commercial purposes onlyProton transfer from strong photoacids to hydroxylic solvents is much under debate. Experimentally, the main issue stems from relaxation and diffusion processes that are concomitant with ultrafast proton transfer and blur population dynamics. To overcome this, we propose a fast photodissociation reaction that, however, proceeds slower than solvent relaxation. Fluorescence spectroscopy of the cationic photoacid 2-(1′-hydroxy-2′-naphtyl)benzimidazolium reveals a two-stage mechanism: (a) reversible elementary proton transfer inside the solvent shell and (b) irreversible contact-pair splitting. The time evolution of the fluorescence signal is complex, yet this is explained quantitatively by simultaneous, spectrally overlapping emission of the acid, the conjugate base, and the contact proton-transfer pair. The latter attains high transient concentration in linear alcohols. Microscopic rate constants of dissociation are determinedWe thank the Spanish Government and the European Regional Development Fund (Grants CTQ2010-17835 and CTQ2010-17026) and the Xunta de Galicia (Grants CN 2012/314,EM2012/091, and GPC2013/052) for financial support of our work. J.L.P.L. thanks the Spanish Ministry of Economy and Competitiveness for funding through the Ramón y Cajal Programm 2009. M.V.G. and A.B. thank the Spanish Government and the “Segundo Gil-Dávila” Foundation, respectively, for financial supportS

Dissociation of a Strong Acid in Neat Solvents: Diffusion Is Observed after Reversible Proton Ejection Inside the Solvent Shell

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry B 2013, 117, 14065–14078, DOI: 10.1021/jp4042765, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jp4042765. This article may be used for non-commercial purposes onlyStrong-acid dissociation was studied in alcohols. Optical excitation of the cationic photoacid N-methyl-6-hydroxyquinolinium triggers proton transfer to the solvent, which was probed by spectral reconstruction of picosecond fluorescence traces. The process fulfills the classical Eigen–Weller mechanism in two stages: (a) solvent-controlled reversible dissociation inside the solvent shell and (b) barrierless splitting of the encounter complex. This can be appreciated only when fluorescence band integrals are used to monitor the time evolution of the reactant and product concentrations. Band integrals are insensitive to solvent dynamics and report relative concentrations directly. This was demonstrated by first measuring the fluorescence decay of the conjugate base across the full emission band, independently of the proton-transfer reaction. Multiexponential decay curves at single wavelengths result from a dynamic red shift of fluorescence in the course of solvent relaxation, whereas clean single exponential decays are obtained if the band integral is monitored instead. The extent of the shift is consistent with previously reported femtosecond transient absorption measurements, continuum theory of solvatochromism, and molecular properties derived from quantum chemical calculations. In turn, band integrals show clean biexponential decay of the photoacid and triexponential evolution of the conjugate base in the course of the proton transfer to solvent reaction. The dissociation step follows the slowest stage of solvation, which was measured here independently by picosecond fluorescence spectroscopy in five aliphatic alcohols. Also, the rate constant of the encounter-complex splitting stage is compatible with proton diffusion. Thus, for this photoacid, both stages reach the highest possible rates: solvation and diffusion control. Under these conditions, the concentration of the encounter complex is substantial during the earliest nanosecondWe thank the Spanish Government and the European Regional Development Fund (grant nos. CTQ2010-17835, CTQ2010-17026, and CTQ2011-29311-C02-01) and the Xunta de Galicia (grants nos. CN 2012/314, 2012-PG237, GPC2013/052 and INCITE09 314 252 PR) for financial support of our work. J.L.P.L. thanks the Spanish Ministry of Economy and Competitiveness for funding through the Ramon y Cajal ́ Programm 2009. M.V. and C.C.B. thank the Spanish Government for funding through the FPU program. A. B. thanks the Segundo Gil Dávila Foundation for financial supportS