Population Of Triplet State Research Articles

Magnetic field effect on ion pair dynamics upon bimolecular photoinduced electron transfer in solution.

The dynamics of the ion pairs produced upon fluorescence quenching of the electron donor 9,10-dimethylanthracene (DMeA) by phthalonitrile have been investigated in acetonitrile and tetrahydrofuran using transient absorption spectroscopy. Charge recombination to both the neutral ground state and the triplet excited state of DMeA is observed in both solvents. The relative efficiency of the triplet recombination pathway decreases substantially in the presence of an external magnetic field. These results were analyzed theoretically within the differential encounter theory, with the spin conversion of the geminate ion pairs described as a coherent process driven by the hyperfine interaction. The early temporal evolution of ion pair and triplet state populations with and without magnetic field could be well reproduced in acetonitrile, but not in tetrahydrofuran where fluorescence quenching involves the formation of an exciplex. A description of the spin conversion in terms of rates, i.e., incoherent spin transitions, leads to an overestimation of the magnetic field effect.

Mechanistic insight into photocrosslinking reaction between triplet state 4-thiopyrimidine and thymine.

4-Thiopyrimidine (e.g., 4-thiouracil (4-TU) and 4-thiothymine (4-TT)) is a typical kind of thiobase. With the sulfur substitution at the C4 position of the canonical pyrimidine nucleobase, 4-thiopyrimidine displays unique photophysical and photochemical properties such as red-shifted maximum absorption peaks and efficient triplet state populations. One of the properties is the photocrosslinking reaction between 4-thiopyrimidine and pyrimidine base, which plays important roles in photochemotherapy and photolabeling applications. By using density functional theory (M06-2X), we have explored the potential energy profiles of the photocrosslinking reaction between 4-thiopyrimidine (4-TU and 4-TT) and thymine in the S0 and T1 states as well as the interaction between the two states. For both (6-4) and (5-4) photocrosslinking reactions, multiple nonadiabatic pathways via minimum energy crossing points (MECPs) between potential surfaces (PESs) of the T1 and S0 states greatly facilitate the proceeding of photocrosslinking reactions and lead to the relatively stable thietane intermediate in the S0 state. The subsequent H migration in the thietane intermediate takes place solely in the S0 state with surmountable energy barriers in bulk solution, resulting in the formation of the photocrosslinked product. This research provides not only a new mechanistic insight into the photocrosslinking reaction for 4-thiopyrimidines but also a rational explanation for the experiments of UVA irradiated Tp4ST dinucleotide and 4-thiothymidine-containing oligonucleotides, facilitating the deep understanding of the synergistic cytotoxicity of 4-thiopyrimidines and UVA as well as the development of alternative phototherapeutic agents and photolabeling probes.

Nonlinear optical behavior of n-tuple decker phthalocyanines at the nanosecond regime: investigation of change in mechanisms.

The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.

Salt Effect in Ion-Pair Dynamics after Bimolecular Photoinduced Electron Transfer in a Room-Temperature Ionic Liquid.

Bimolecular photoinduced electron transfer between perylene and two quenchers was investigated in an imidazolium room-temperature ionic liquid (RTIL) and in a dipolar solvent mixture of the same viscosity using transient absorption on the subpicosecond to submicrosecond time scales. Whereas charge separation dynamics were similar in both solvents, significant differences were observed in the temporal evolution of the ensuing radical ions: although small, the free-ion yield is significantly larger in the RTIL, and recombination of the ion pair to the triplet state of perylene is more efficient in the dipolar solvent. The temporal evolution of reactant, ion, and triplet state populations could be well reproduced using unified encounter theory. This analysis reveals that the observed differences can be explained by the strong screening of the Coulomb potential in the ion pair by the ionic solvent. In essence, RTILs favor free ions compared to highly dipolar solvents of the same viscosity.

Photo-Induced Charge Separation vs. Degradation of a BODIPY-Based Photosensitizer Assessed by TDDFT and RASPT2

A meso-mesityl-2,6-iodine substituted boron dipyrromethene (BODIPY) dye is investigated using a suite of computational methods addressing its functionality as photosensitizer, i.e., in the scope of light-driven hydrogen evolution in a two-component approach. Earlier reports on the performance of the present iodinated BODIPY dye proposed a significantly improved catalytic turn-over compared to its unsubstituted parent compound based on the population of long-lived charge-separated triplet states, accessible due to an enhanced spin-orbit coupling (SOC) introduced by the iodine atoms. The present quantum chemical study aims at elucidating the mechanisms of both the higher catalytic performance and the degradation pathways. Time-dependent density functional theory (TDDFT) and multi-state restricted active space perturbation theory through second-order (MS-RASPT2) simulations allowed identifying excited-state channels correlated to iodine dissociation. No evidence for an improved catalytic activity via enhanced SOCs among the low-lying states could be determined. However, the computational analysis reveals that the activation of the dye proceeds via pathways of the (prior chemically) singly-reduced species, featuring a pronounced stabilization of charge-separated species, while low barriers for carbon-iodine bond breaking determine the photostability of the BODIPY dye.

Photochemical and Photodynamical Properties of Sulfur‐Substituted Nucleic Acid Bases,

Sulfur-substituted nucleobases (a.k.a., thiobases) are among the world's leading prescriptions for chemotherapy and immunosuppression. Long-term treatment with azathioprine, 6-mercaptopurine and 6-thioguanine has been correlated with the photoinduced formation of carcinomas. Establishing an in-depth understanding of the photochemical properties of these prodrugs may provide a route to overcoming these carcinogenic side effects, or, alternatively, a basis for developing effective compounds for targeted phototherapy. In this review, a broad examination is undertaken, surveying the basic photochemical properties and excited-state dynamics of sulfur-substituted analogs of the canonical DNA and RNA nucleobases. A molecular-level understanding of how sulfur substitution so remarkably perturbs the photochemical properties of the nucleobases is presented by combining experimental results with quantum-chemical calculations. Structure-property relationships demonstrate the impact of site-specific sulfur substitution on the photochemical properties, particularly on the population of the reactive triplet state. The value of fundamental photochemical investigations for driving the development of ultraviolet-A chemotherapeutics is showcased. The most promising photodynamic agents identified thus far have been investigated in various carcinoma cell lines and shown to decrease cell proliferation upon exposure to ultraviolet-A radiation. Overarching principles have been elucidated for the impact that sulfur substitution of the carbonyl oxygen has on the photochemical properties of the nucleobases.

Solvation effects alter the photochemistry of 2-thiocytosine

Radiationless deactivation channels of 2-thiocytosine in aqueous environment are revisited by means of quantum-chemical simulations of excited-state absorption spectra, and investigations of potential energy surfaces of the chromophore clustered with two water molecules using the algebraic diagrammatic construction method to the second-order (ADC(2)), and multireference configuration interaction with single and double excitations (MR-CISD) methods. We argue that interactions of explicit water molecules with thiocarbonyl group might enable water-chromophore electron transfer (WCET) which leads to formation of intersystem crossing that was not considered previously. This is the first example of a WCET process occurring in the triplet manifold of electronic states. This phenomenon might explain nonradiative decay of the triplet state population observed in thiopyrimidines in the absence of molecular oxygen. According to our calculations this WCET process might also entail a subsequent, virtually barrierless, electron-driven proton transfer (EDPT) resulting in the formation of hydroxyl radical which could further participate in photohydration or deamination reactions.

Dithionated Nucleobases as Effective Photodynamic Agents against Human Epidermoid Carcinoma Cells

Sulfur-substituted nucleobases (i.e., thiobases) are a prospective class of compounds for clinical and cosmetic topical phototherapies. Recent investigations of several thiobases have revealed the ultrafast and efficient population of reactive triplet states upon ultraviolet-A (UVA) irradiation and the subsequent generation of singlet oxygen in high yield. In this contribution, we examine the photosensitizing activities of three of the most promising thiobase derivatives discovered to date: 2,4-dithiothymine, 2,4-dithiouracil, and 2,6-dithiopurine. These derivatives are shown to decrease the proliferation of human epidermoid carcinoma cells by up to 63 % in vitro, only upon activation with a low dose of UVA radiation (5 J cm-2 ). The generation of reactive oxygen species plays a minor role in the mode of action, suggesting these dithiobases may be effective within oxygen-deficient environments. Importantly, the photosensitized activity correlates with the magnitude of the triplet lifetime, which should guide the molecular design of next-generation photodynamic agents.

Theoretical Insights into the Switching Off/On of 1 O2 Photosensitization in Chemicontrolled Photodynamic Therapy.

Density Functional Theory and time-dependent (TD) DFT calculations were carried out for recently reported 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based photosensitizers (PSs) that could be activated by reactive oxygen species (ROS) to generate 1 O2 specifically in target tissues. To assess the applicability of the compounds as activatable PSs (a-PSs) in photodynamic therapy, absorption wavelengths; singlet-triplet energy gaps; and spin-orbit matrix elements for the radiationless transition, Sn →Tm , were investigated. A TD-DFT qualitative analysis indicated that only a Br-substituted BODIPY derivative with the chromanol ring of α-tocopherol linked by methylene functioned as an a-PS. The chromanol ring promotes photoinduced electron transfer to the BODIPY unit that reduces the probability of intersystem crossing and triplet-state population, and can turn off 1 O2 photosensitization. Therefore, 1 O2 photosensitization can be switched on only in target cells in which the chromanol ring is oxidized by ROS. The oxidation reaction pathways of the most promising derivative, by either 1 O2 or cumyloxyl radical as typical ROS, have been examined to reveal that oxidation by the cumyloxyl radical is more effective than that by 1 O2 .

Detection of ultra-low oxygen concentration based on the fluorescence blinking dynamics of single molecules

We present a sensitive method for detection of ultra-low oxygen concentrations based on the fluorescence blinking dynamics of single molecules. The relationship between the oxygen concentration and the fraction of time spent in the off-state, stemming from the population and depopulation of triplet states and radical cationic states, can be fitted with a two-site quenching model in the Stern-Volmer plot. The oxygen sensitivity is up to 43.42 kPa−1 in the oxygen partial pressure region as low as 0.01–0.25 kPa, which is seven times higher than that of the fluorescence intensity indicator. This method avoids the limitation of the sharp and non-ignorable fluctuations that occur during the measurement of fluorescence intensity, providing potential applications in the field of low oxygen-concentration monitoring in life science and industry.

Photosensitization Versus Photocyclization: Competitive Reactions of Phenylphenalenone in Its Role as Phytoanticipins in Plant Defense Strategies.

Phenalenone (PN) derivatives are involved in plant defense strategies, producing molecular singlet oxygen in a photosensitization process. Many experimental and theoretical studies determined that PN can performe this process with a quantum yield close to 1. However, it has been observed that the efficiency of some of its derivatives is much lower. This is the case of 9-phenylphenalenone (9-PhPN). To elucidate the factors that determine the different photochemistry of PN and its derivate 9-PhPN, we developed a complete active space self-consistent field/multi-configurational second-order perturbation theory study where several deactivation paths through the lowest excited states were explored. We found that the characteristics of the low-lying excited states are similar for both PN and 9-PhPN in the areas near the geometry of excitation. Consequently, the first processes that take place immediately after absorption are possible in both systems, including the population of the triplet state responsible for oxygen sensitization. However, 9-PhPN can also undergo cyclization by a bond formation between the carbonyl oxygen and a carbon atom of the phenyl substituent. This process competes favorably with population of triplet states and is responsible for the decrease of the quantum yield of oxygen sensitization in 9-PhPN relative to PN.

Effect of heavy atoms on photochemically induced dynamic nuclear polarization in liquids

Given its short hyperpolarization time (∼10−6 s) and mostly non-perturbative nature, photo-chemically induced dynamic nuclear polarization (photo-CIDNP) is a powerful tool for sensitivity enhancement in nuclear magnetic resonance. In this study, we explore the extent of 1H-detected 13C nuclear hyperpolarization that can be gained via photo-CIDNP in the presence of small-molecule additives containing a heavy atom. The underlying rationale for this methodology is the well-known external-heavy-atom (EHA) effect, which leads to significant enhancements in the intersystem-crossing rate of selected photosensitizer dyes from photoexcited singlet to triplet. We exploited the EHA effect upon addition of moderate amounts of halogen-atom-containing cosolutes. The resulting increase in the transient triplet-state population of the photo-CIDNP sensitizer fluorescein resulted in a significant increase in the nuclear hyperpolarization achievable via photo-CIDNP in liquids. We also explored the internal-heavy-atom (IHA) effect, which is mediated by halogen atoms covalently incorporated into the photosensitizer dye. Widely different outcomes were achieved in the case of EHA and IHA, with EHA being largely preferable in terms of net hyperpolarization.

Singlet Fission Reaction of Light-Exposed β-Carotene Bound to Bovine Serum Albumin. A Novel Mechanism in Protection of Light-Exposed Tissue by Dietary Carotenoids.

We have attempted to investigate the role of carotenoids (Car) in protecting pigment-protein complexes against light-induced degradation. Upon direct photoexcitation of β-carotene (β-Car), nanosecond flash photolysis and femtosecond time-resolved spectroscopy detected a substantial population of triplet states for β-Car aggregates associated with bovine serum albumin (BSA) or dispersed in aqueous phase with 10% tetrahydrofuran (THF), but none were observed for monomeric β-Car in neat THF. The direct photogeneration of triplet states was on the time scale of <1 ps, indicating that the underlying reaction mechanism was singlet fission (SF). Efficient triplet-triplet annihilation in the time regime from picoseconds to microseconds resulted in a <1 μs triplet lifetime for β-Car aggregates, in contrast to a 20 μs lifetime for monomeric β-Car as determined by anthracene-sensitized flash photolysis. The short-lived triplet excitations of β-Car aggregates associated with BSA or dispersed in aqueous phase were found to be insensitive to the presence of oxygen, which are considered to be important for the protection of both protein and carotenoid against light-induced degradation via reaction with oxidative species.

Metal Atom Effect on the Photophysical Properties of Mg(II), Zn(II), Cd(II), and Pd(II) Tetraphenylporphyrin Complexes Proposed as Possible Drugs in Photodynamic Therapy

The effects of Mg, Zn, Cd, and Pd dications on the photophysical properties of the tetraphenylporphyrin ligand have been explored, considering the corresponding complexes and by using the density functional theory and its time-dependent extension. Results show that absorption wavelengths do not change significantly when the metal ion changes contrary to what happens to the singlet–triplet energy gaps (ΔES−T) and the spin-orbit matrix elements . The most probable intersystem spin crossing (ISC) pathways for the population of the lowest triplet states have been explored. Our findings can contribute to rationalize the available experimental data and promote the potential therapeutic use of these compounds as photosensitizers in photodynamic therapy (PDT).

Measurement of oxygen concentrations in bacterial biofilms using transient state monitoring by single plane illumination microscopy

Oxygen is required for respiration in aerobic bacteria and hence plays an essential role in the generation of energy necessary for cell maintenance and growth. The distribution of oxygen within a biofilm can be heterogeneous and may result in bacterial cells exhibiting distinct physiological states depending on their local oxygen availability. Here, we have employed transient state (TRAST) monitoring, a non-invasive method that can measure the relative populations of triplet states by time-modulated illumination, to determine the distribution of oxygen concentrations in biofilm colonies. The method was implemented on a single plane illumination microscope that can perform optical slicing, making it a suitable approach for imaging thick samples. We present a map of triplet relaxation times measured inside a Pseudomonas aeruginosa biofilm at micrometre resolution. We also provide a calibration method that can evaluate oxygen concentration based on TRAST contrast. Our results indicate that anoxic zones exist within the colonies, and oxygen consumption extends outside the areas of high cell densities, establishing a gradient until levels return to air saturation.

Triplet versus singlet chemiexcitation mechanism in dioxetanone: a CASSCF/CASPT2 study

Chemiluminescence is a fundamental process of chemistry consisting in the conversion of chemical energy stored in chemical bonds into light. It is used by nature and by man-made technology, being especially relevant in chemical analysis. The understanding of the phenomenon strongly relies in the study of peroxide models such as 1,2-dioxetanones. In the present contribution, the singlet S 2 and the triplet T 2 potential energy surfaces of the unimolecular decomposition of 1,2-dioxetanone have been mapped along the O–O and C–C bond coordinates on the grounds of the multiconfigurational CASPT2//CASSCF approach. Results confirm the energy degeneracy between T 2, T 1, S 1, and S 0 at the TS region, whereas S 2 is unambiguously predicted at higher energies. Triplet-state population is also supported by the spin–orbit couplings between the singlet and triplet states partaking in the process. In particular, the first-principle calculations show that decomposition along the T 2 state is a competitive process, having a small (~3 kcal/mol) energy barrier from the ground-state TS structure. The present findings can explain the higher quantum yield of triplet-state population with respect to the excited singlet states recorded experimentally for the unimolecular decomposition of 1,2-dioxetanone models.

A new approach to molecular dynamics with non-adiabatic and spin-orbit effects with applications to QM/MM simulations of thiophene and selenophene.

We present surface hopping dynamics on potential energy surfaces resulting from the spin-orbit splitting, i.e., surfaces corresponding to the eigenstates of the total electronic Hamiltonian including the spin-orbit coupling. In this approach, difficulties arise because of random phases of degenerate eigenvectors and possibility of crossings of the resulting mixed states. Our implementation solves these problems and allows propagation of the coefficients both in the representation of the spin free Hamiltonian and directly in the "diagonal representation" of the mixed states. We also provide a detailed discussion of the state crossing and point out several peculiarities that were not mentioned in the previous literature. We also incorporate the effect of the environment via the quantum mechanics/molecular mechanics approach. As a test case, we apply our methodology to deactivation of thiophene and selenophene in the gas phase, ethanol solution, and bulk liquid phase. First, 100 trajectories without spin-orbit coupling have been calculated for thiophene starting both in S1 and S2 states. A subset of 32 initial conditions starting in the S2 state was then used for gas phase simulations with spin-orbit coupling utilizing the 3-step integrator of SHARC, our implementation of the 3-step propagator in Newton-X and two new "one-step" approaches. Subsequently, we carried out simulations in ethanol solution and bulk liquid phase for both thiophene and selenophene. For both molecules, the deactivation of the S2 state proceeds via the ring opening pathway. The total population of triplet states reaches around 15% and 40% after 80 fs for thiophene and selenophene, respectively. However, it only begins growing after the ring opening is initiated; hence, the triplet states do not directly contribute to the deactivation mechanism. For thiophene, the resulting deactivation lifetime of the S2 state was 68 fs in the gas phase, 76 fs in ethanol solution, and 78 fs in the liquid phase, in a good agreement with the experimental value of 80 fs (liquid phase). For selenophene, the obtained S2 lifetime was 60 fs in the gas phase and 62 fs for both ethanol solution and liquid phase. The higher rate of intersystem crossing to the triplet states in selenophene is likely the reason for the lower fluorescence observed in selenium containing polymer compounds.

Photophysical Properties of S, Se and Te-Substituted Deoxyguanosines: Insight into Their Ability To Act as Chemotherapeutic Agents.

Guanine and guanosine derivatives have long been in use as anticancer drugs and recently have been proposed also as photosensitizers in photodynamic therapy. By means of density functional theory and its time-dependent formulation, the potential power as UVA chemotherapeutic agents has been investigated computing the photophysical properties (absorption spectra, excitation energies, and spin-orbit matrix elements) of sulfur, selenium, and tellurium-substituted deoxyguanosines. Different pathways for the population of the lowest triplet state have been considered. Results show that all the examined systems have the lowest triplet state lying above the energy required for the production of the highly cytotoxic excited molecular oxygen 1Δg and that the heavy atom effect ensures an efficient intersystem spin crossing.

Photoinduced C—I bond homolysis of 5-iodouracil: A singlet predissociation pathway

5-Iodouracil (5-IU) can be integrated into DNA and acts as a UV sensitive chromophore suitable for probing DNA structure and DNA-protein interactions based on the photochemical reactions of 5-IU. Here, we perform joint studies of time-resolved Fourier transform infrared (TR-FTIR) spectroscopy and ab initio calculations to examine the state-specific photochemical reaction mechanisms of the 5-IU. The fact that uracil (U) is observed in TR-FTIR spectra after 266 nm irradiation of 5-IU in acetonitrile and ascribed to the product of hydrogen abstraction by the uracil-5-yl radical (U·) provides experimental evidence for the C-I bond homolysis of 5-IU. The excited state potential energy curves are calculated with the complete active space second-order perturbation//complete active space self-consistent field method, from which a singlet predissociation mechanism is elucidated. It is shown that the initially populated 1(ππ*) state crosses with the repulsive 1(πσ*) or 1(nIσ*) state, through which 5-IU undergoes dissociation to the fragments of (U·) radical and iodine atom. In addition, the possibility of intersystem crossing (ISC) is evaluated based on the calculated vertical excitation energies. Although a probable ISC from 1(ππ*) state to 3(nOπ*) and then to the lowest triplet 3(ππ*) could occur in principal, there is little possibility for the excited state populations bifurcating to triplet manifold, given that the singlet state predissociation follows repulsive potential and should occur within dozens to hundreds of femtoseconds. Such low population of triplet states means that the contribution of triplet state to photoreactions of 5-IU should be quite minor. These results demonstrate clearly a physical picture of C-I bond homolysis of 5-IU and provide mechanistic illuminations to the interesting applications of 5-IU as photoprobes and in radiotherapy of cancer.

Halogen atom effect on the photophysical properties of substituted aza-BODIPY derivatives.

The influence of halogen atom substitution (Br and I), in different amounts and positions in an aza-BODIPY skeleton, on the photophysical properties of some aza-BODIPY derivatives has been investigated by using density functional theory and its time-dependent extension. The heavy atom effect on excitation energies, singlet-triplet energy gaps and spin-orbit matrix elements has been considered. The maximum absorption within the therapeutic window has been confirmed for all the aza-BODIPY derivatives. The feasible intersystem spin crossing pathways for the population of the lowest triplet state, that will depend on the values of the spin-orbit matrix elements, the energy gap as well as the orbital composition of the involved states have been found to most likely involve the S1 and T1 or T2 states. The outcomes of computations support the potential therapeutic use of these compounds as photosensitizers in photodynamic therapy.