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Molecular oxygen, O2, has long provided a cornerstone for studies in chemistry, physics, and biology. Although the triplet ground state, O2(X3Σg-), has garnered much attention, the lowest excited electronic state, O2(a1Δg), commonly called singlet oxygen, has attracted appreciable interest, principally because of its unique chemical reactivity in systems ranging from the Earth's atmosphere to biological cells. Because O2(a1Δg) can be produced and deactivated in processes that involve light, the photophysics of O2(a1Δg) are equally important. Moreover, pathways for O2(a1Δg) deactivation that regenerate O2(X3Σg-), which address fundamental principles unto themselves, kinetically compete with the chemical reactions of O2(a1Δg) and, thus, have practical significance. Due to technological advances (e.g., lasers, optical detectors, microscopes), data acquired in the past â¼20 years have increased our understanding of O2(a1Δg) photophysics appreciably and facilitated both spatial and temporal control over the behavior of O2(a1Δg). One goal of this Review is to summarize recent developments that have broad ramifications, focusing on systems in which oxygen forms a contact complex with an organic molecule M (e.g., a liquid solvent). An important concept is the role played by the M+â¢O2-⢠charge-transfer state in both the formation and deactivation of O2(a1Δg).
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2,5-Bis(phenylethynyl) rhodacyclopentadienes (RCPDs), as a type of Rh(iii) complex, exhibit unusually intense fluorescence and slow intersystem crossing (ISC) due to weak metal-ligand interactions. However, details on their ultrafast photophysics and ISC dynamics are limited. In this work, electronic relaxation upon photoexcitation of two substituted RCPDs with two -CO2Me (A-RC-A) or -NMe2/-CO2Me (D-RC-A) end groups are comprehensively investigated using femtosecond transient absorption spectroscopy and theoretical analysis. Upon ultraviolet and visible excitation, dephasing of vibrational coherence, charge transfer, conformation relaxation, and ISC are observed experimentally. By calculating the spin-orbit coupling, reorganization energy, and adiabatic energy gap of plausible ISC channels, semi-classical Marcus theory revealed the dominance of thermally activated ISC (S1 â T2) for both D-RC-A and A-RC-A, while S1 â T1 channels are largely blocked due to high ISC barriers. With weak spin-orbit coupling, such differences in plausible ISC channels are predominately tuned by energetic parameters. Singlet oxygen sensitization studies of A-RC-A provide additional insight into the excited-state behavior of this complex.
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With few exceptions, triplet excited states of organic molecules, 3M1, are quenched by ground state molecular oxygen, O2(X3Σg-), with rate constants kq greater than â¼109 M-1 s-1 in fluid solutions. If the energy of the triplet state is above 94 kJ/mol, then such quenching can result in the sensitized production of singlet oxygen, O2(a1Δg). In the interaction between 3M1 and O2(X3Σg-), the magnitudes of both kq and the yield of the O2(a1Δg) depend appreciably on mixing with the M-O2 charge-transfer state. Here, we report that triplet states of several thioxanthen-9-one-10,10-dioxide derivatives have unusually low kq values (as low as â¼1 × 108 M-1 s-1) but have quantum yields for the photosensitized production of O2(a1Δg) that approach unity. Because these molecules possess high oxidation potentials (â¼3.5 V vs SCE), we suggest that charge transfer character in the 3M1-O2(X3Σg-) encounter complex is reduced, thereby lowering kq while maintaining high O2(a1Δg) yields. These results provide important experimental support for existing models for the quenching of organic molecule excited states by O2(X3Σg-).
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Disulfide bonds are critical structural elements in proteins and stabilize folded structures. Modification of these linkages is associated with a loss of structure and function. Previous studies have reported large variations in the rate of disulfide oxidation by hypohalous acids, due to stabilization of reaction intermediates. In this study we hypothesized that considerable variation (and hence selective oxidation) would occur with singlet oxygen (1O2), a key intermediate in photo-oxidation reactions. The kinetics of disulfide-mediated 1O2 removal were monitored using the time-resolved 1270 nm phosphorescence of 1O2. Stern-Volmer plots of these data showed a large variation (â¼103) in the quenching rate constants kq (from 2 × 107 for α-lipoic acid to 3.6 × 104 M-1s-1 for cystamine). The time course of disulfide loss and product formation (determined by LC-MS) support a role for 1O2, with mono- and di-oxygenated products detected. Elevated levels of these latter species were generated in D2O- compared to H2O buffers, which is consistent with solvent effects on the 1O2 lifetime. These data are interpreted in terms of the intermediacy of a zwitterion [-S+(OO-)-S-], which either isomerizes to a thiosulfonate [-S(O)2-S-] or reacts with another parent molecule to give two thiosulfinates [-S(O)-S-]. The variation in quenching rates and product formation are ascribed to zwitterion stabilization by neighboring, or remote, lone pairs of electrons. These data suggest that some disulfides, including some present within or attached to proteins (e.g., α-lipoic acid), may be selectively modified, and undergo subsequent cleavage, with adverse effects on protein structure and function.
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Oxígeno Singlete , Ácido Tióctico , Péptidos , Cromatografía Liquida , DisulfurosRESUMEN
One key challenge in the development of viable organic photovoltaic devices is to design component molecules that do not degrade during combined exposure to oxygen and light. Such molecules should thus remain comparatively unreactive towards singlet molecular oxygen and not act as photosensitizers for the generation of this undesirable species. Here, novel redox-active chromophores that combine these two properties are presented. By functionalizing indenofluorene-extended tetrathiafulvalenes (IF-TTFs) with cyano groups at the indenofluorene core using Pd-catalyzed cyanation reactions, we find that the reactivity of the exocyclic fulvene carbon-carbon double bonds towards singlet oxygen is considerably reduced. The new cyano-functionalized IF-TTFs were tested in non-fullerene acceptor based organic photovoltaic proof-of-principle devices, revealing enhanced device stability.
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Oxígeno , Oxígeno Singlete , Oxígeno Singlete/química , Fármacos Fotosensibilizantes/química , CarbonoRESUMEN
Singlet oxygen, O2(a1Δg), the lowest excited electronic state of molecular oxygen, plays an important role in a range of chemical and biological processes. In liquid solvents, the reactions of singlet oxygen with a solute kinetically compete with solvent-mediated deactivation that yields the ground electronic state of oxygen, O2(X3Σg-). In this regard, the key parameter is the solvent-mediated lifetime of singlet oxygen, which embodies fundamental physical principles ranging from intermolecular interactions that perturb the forbidden O2(a1Δg) â O2(X3Σg-) transition to the transfer of oxygen's excitation energy into the vibrational modes of a solvent molecule M. Extensive research performed by the global community on this oxygen-related issue over the past â¼50 years reflects its significance. Unfortunately, a satisfactory quantitative understanding of this unique solvent effect has remained elusive thus far. In temperature-dependent studies, we have quantified the singlet oxygen lifetime in common aromatic and aliphatic organic solvents, including partially deuterated molecules that exploit the H/D solvent isotope effect on the lifetime. We now account for experimental data, including previously intractable data, using a model that exploits both weak and strong coupling in the M-O2 complex to accommodate the roles that M plays to (1) induce the forbidden O2(a1Δg) â O2(X3Σg-) transition and (2) accept the excitation energy of O2(a1Δg). As such, our approach brings us appreciably closer to an accurate and predictive ab initio solution for the long-standing oxygen-dependent problem that, in turn, should be relevant for a host of other molecular systems.
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Oxígeno , Oxígeno Singlete , Oxígeno/química , Oxígeno Singlete/química , Soluciones , Solventes/químicaRESUMEN
Spectra and absorption coefficients of the forbidden 765 nm X3Σg- â b1Σg+ transition of molecular oxygen dissolved in organic solvents at atmospheric pressure were recorded over a 5 m path length using a liquid waveguide capillary cell. The results show that it is possible to investigate this weak near-infrared absorption transition in a common liquid hydrocarbon solvent without the need for a potentially dangerous high oxygen pressure. Proof-of-principle data from benzene, toluene, chlorobenzene, bromobenzene, and iodobenzene reveal a pronounced heavy atom effect on this spin-forbidden transition. For example, the absorption coefficient at the band maximum in iodobenzene, (28.9 ± 3.3) × 10-3 M-1 cm-1, is approximately 21 times larger than that in benzene, (1.4 ± 0.1) × 10-3 M-1 cm-1. These absorption measurements corroborate results obtained from O2(X3Σg-) â O2(b1Σg+) excitation spectra of O2(a1Δg) â O2(X3Σg-) phosphorescence, which depended on data from a plethora of convoluted experiments. Spectroscopic studies of molecular oxygen in liquid solvents can help evaluate aspects of the seminal Strickler-Berg approach to treat the effect of solvent on Einstein's A and B coefficients for radiative transitions. In particular, our present results are a key step toward using the O2(X3Σg-) â O2(b1Σg+) transition to evaluate the speculated limiting condition of applying the Strickler-Berg treatment to a highly forbidden process. This latter issue is but one example of how an arguably simple homonuclear diatomic molecule continues to aid the scientific community by providing fundamental physical insight.
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Perturbation by a neighboring molecule M appreciably alters the properties of both the ground and excited states of molecular oxygen, as reflected in a variety of photophysical phenomena. In this article, we build upon the ~ 100 year history of work in this field, illustrating how the M-O2 system continues to challenge the scientific community, facilitating better insight into fundamental tenets of chemistry and physics.
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Oxígeno , Oxígeno Singlete , Oxígeno/química , Oxígeno Singlete/químicaRESUMEN
Studies of the interactions between molecular oxygen and a perturbing species, such as an organic solvent, have been an active research area for at least 70 years. In particular, interaction with a neighboring molecule or atom may perturb the electronic states of oxygen to such an extent that the O2(a1Δg) â O2(X3Σg-) transition, formally forbidden as an electric dipole process, achieves significant transition probability. We present a computational study of how the geometry of complexes consisting of molecular oxygen and different perturbing species influences the magnitude of spin-orbit coupling that facilitates the O2(a1Δg) â O2(X3Σg-) transition. We rationalize our results using a model based on orbital interactions: a non-zero spin-orbit coupling matrix element results from asymmetric transfer of charge to or from the 1πg orbitals on oxygen. Our results indicate that the atoms in a perturbing species closest to oxygen are responsible for the majority of the spin-orbit interactions, suggesting that large systems can be simplified appreciably. Furthermore, we infer and confirm that an estimate of the spin-orbit coupling matrix element can be obtained from the magnitude of the induced energy splitting of oxygen's 1πg orbitals. These results should provide further momentum in the long-standing issue of understanding phenomena that influence the O2(a1Δg) â O2(X3Σg-) transition.
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An eye lens is constantly exposed to the solar UV radiation, which is considered the most important external source of age-related changes to eye lens constituents. The accumulation of modifications of proteins and lipids with age can eventually lead to the development of progressive lens opacifications, such as cataracts. Though the impact of solar UV radiation on the structure and function of proteins is actively studied, little is known about the effect of photodamage on plasma membranes of lens cells. In this work we exploit Fluorescence Lifetime Imaging Microscopy (FLIM), together with viscosity-sensitive fluorophores termed molecular rotors, to study the changes in viscosity of plasma membranes of porcine eye lens resulting from two different types of photodamage: Type I (electron transfer) and Type II (singlet oxygen) reactions. We demonstrate that these two types of photodamage result in clearly distinct changes in viscosity - a decrease in the case of Type I damage and an increase in the case of Type II processes. Finally, to simulate age-related changes that occur in vivo, we expose an intact eye lens to UV-A light under anaerobic conditions. The observed decrease in viscosity within plasma membranes is consistent with the ability of eye lens constituents to sensitize Type I photodamage under natural irradiation conditions. These changes are likely to alter the transport of metabolites and predispose the whole tissue to the development of pathological processes such as cataracts.
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Cristalino/efectos de la radiación , Rayos Ultravioleta , Animales , Membrana Celular/efectos de la radiación , Técnicas In Vitro , Oxígeno Singlete/metabolismo , Porcinos , ViscosidadRESUMEN
The collision complex between the ground electronic state of an organic molecule, M, and ground state oxygen, O2(X3Σg-), can absorb light to produce an intermolecular charge transfer (CT) state, often represented simply as the M radical cation, M+Ë, paired with the superoxide radical anion, O2-Ë. Aspects of this transition have been the subject of numerous studies for â¼70 years, many of which address fundamental concepts in chemistry and physics. We now examine the extent to which the combination of Molecular Dynamics simulations and electronic structure response methods can model transitions to the toluene-O2 CT state. To account for the experimental spectra, we consider (a) the distribution of toluene-O2 geometries that contribute to the transitions, (b) a quantitative description of intermolecular CT, and (c) oxygen-induced local transitions in toluene that complement the CT transitions, specifically transitions that populate toluene triplet states. We find that the latter oxygen-induced local transitions play a prominent role on the long wavelength side of the spectrum commonly attributed to the intermolecular CT transition. Our calculations provide a new perspective on the seminal discussion between R. S. Mulliken and D. F. Evans on the nature of O2-dependent transitions in organic molecules, and bode well for modeling transitions to excited states with CT character in noncovalent weakly-bonded molecular complexes.
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Protein-encased chromophores that photosensitize the production of reactive oxygen species, ROS, have been the center of recent activity in studies of oxidative stress. One potential attribute of such systems is that the local environment surrounding the chromophore, and that determines the chromophore's photophysics, ideally remains constant and independent of the global environment into which the system is placed. Therefore, a protein-encased sensitizer localized in the mitochondria would arguably have the same photophysics as that protein-encased sensitizer at the plasma membrane, for example. One thus obtains a useful tool to study processes modulated by spatially localized ROS. One ROS of interest is singlet oxygen, O2 (a1 Δg ). We recently developed a singlet oxygen photosensitizing protein, SOPP, in which flavin mononucleotide, FMN, is encased in a re-engineered light-oxygen-voltage protein. One goal was to ascertain how a version of this system, SOPP3, which selectively makes O2 (a1 Δg ), in vitro, behaves in a cell. We now demonstrate that SOPP3 undergoes exacerbated irradiation-mediated bleaching when expressed at either the plasma membrane or mitochondria in stable cell lines. We find that the environment around the SOPP3 system affects the bleaching rate, which argues against one of the key suppositions in support of a protein-encased chromophore.
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Fármacos Fotosensibilizantes , Oxígeno Singlete , Oxígeno/metabolismo , Fármacos Fotosensibilizantes/metabolismo , Fármacos Fotosensibilizantes/farmacología , Proteínas , Especies Reactivas de Oxígeno , Oxígeno Singlete/metabolismo , TransfecciónRESUMEN
Halogenated and nitro ß-carboline (ßCs) alkaloids have garnered increasing interest for their role in a broad range of biological, pharmacological and biotechnological processes. Addressing their spectroscopic and photophysical properties provide tools to further explore the presence of these alkaloids in complex biological matrices. In addition, these studies help to elucidate processes where these alkaloids are involved. The UV-visible and steady-state room temperature fluorescence of bromo- and nitro-harmines in an aqueous environment at different pHs, low-temperature phosphorescence (at 77 K) and quantum yields of singlet oxygen production are reported herein. Singlet (S0 and S1) and triplet (T1) electronic states are further analyzed using density functional theory (DFT) and the results compared with experimental data. Data are discussed in the framework of potential biotechnological applications of these ßC alkaloids.
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Teoría Funcional de la Densidad , Harmina/química , Espectrometría de Fluorescencia , Espectrofotometría Ultravioleta , Agua/químicaRESUMEN
Genetically encodable proteins that photosensitize the production of singlet oxygen, O2(a1Δg), will play an increasingly important role in elucidating mechanisms of cellular processes modulated by reactive oxygen species, ROS, and changes in redox balance. In the development of such tools, it is essential to characterize the oxygen-dependent photophysics of the protein-encased chromophore. Of the O2(a1Δg)-photosensitizing systems recently developed, a protein-bound derivative of Malachite Green has several desirable features: (1) it absorbs light at wavelengths longer than those typically absorbed by endogenous molecules, and (2) the chromophore becomes a viable sensitizer only when bound to the activating protein. However, we now demonstrate that the photophysics of this Malachite Green system is not simple. Our data indicate that, with an increase in the concentration of ground-state oxygen, O2(X3Σg-), the yield of O2(a1Δg) does not increase in a proportional manner. Moreover, the lifetime of O2(a1Δg) decreases as the O2(X3Σg-) concentration is increased. One mechanism that could account for our observations involves the concomitant photo-initiated formation of O2(a1Δg) and the superoxide radical anion. We propose that the superoxide ion acts as a dynamic diffusion-dependent quencher to influence the O2(a1Δg) lifetime and as a static quencher within the protein enclosure to influence the measured O2(a1Δg) yield. Thus, in the least, caution should be exercised when using this Malachite Green system to probe mechanisms of ROS-mediated processes. Our results contribute to a better understanding of the general photophysics of protein-bound O2(a1Δg) sensitizers which, in turn, facilitates the further development of these useful mechanistic tools.
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Proteínas/química , Colorantes de Rosanilina/química , Oxígeno Singlete/metabolismo , Cinética , Luz , Oxígeno/química , Fármacos Fotosensibilizantes/química , Teoría CuánticaRESUMEN
Photochemical and mechanical stability are critical in the production and application of organic solar cells. While these factors can individually be improved using different additives, there is no example of studies on the combined effects of such additive-assisted stabilization. In this study, the properties of PTB7:[70]PCBM organic solar cells are studied upon implementation of two additives: the carotenoid astaxanthin (AX) for photochemical stability and the silicone polydimethylsiloxane (PDMS) for improved mechanical properties. A newly designed additive, AXcPDMS, based on astaxanthin covalently bonded to PDMS was also examined. Lifetime tests, produced in ISOS-L-2 conditions, reveal an improvement in the accumulated power generation (APG) of 10% with pure AX, of 90% when AX is paired with PDMS, and of 140% when AXcPDMS is added in the active layer blend, as compared to the control devices. Singlet oxygen phosphorescence measurements are utilized to study the ability of AX and AXcPDMS to quench singlet oxygen and its precursors in the films. The data are consistent with the strong stabilization effect of the carotenoids. While AX and AXcPDMS are both efficient photochemical stabilizers, the improvement in device stability observed in the presence of AXcPDMS is likely due to a more favorable localization of the stabilizer within the blend. The mechanical properties of the active layers were investigated by tensile testing and cohesive fracture measurements, showing a joint improvement of the photooxidative stability and the mechanical properties, thus yielding organic solar cell devices that are promising for flexible photovoltaic applications.
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Fluorescein, and derivatives of fluorescein, are often used as fluorescent probes and sensors. In systems where pH is a variable, protonation/deprotonation of the molecule can influence the pertinent photophysics. Fluorination of the xanthene moiety can alter the molecule's pKa such as to render a probe whose photophysics remains invariant over a wide pH range. Di-fluorination is often sufficient to accomplish this goal, as has been demonstrated with compounds such as Oregon Green in which the xanthene moiety is symmetrically difluorinated. In this work, we synthesized a non-symmetrical difluorinated analog of Oregon Green which we call Athens Green. We ascertained that the photophysics and photochemistry of Athens Green, including the oxygen-dependent photophysics that results in the sensitized production of singlet oxygen, O2(a1Δg), can differ appreciably from the photophysics of Oregon Green. Our data indicate that Athens Green will be a more benign fluorescent probe in systems that involve the production and removal of O2(a1Δg). These results expand the available options in the toolbox of fluorescein-based fluorophores.
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Selenium compounds have been identified as potential oxidant scavengers for biological applications due to the nucleophilicity of Se, and the ease of oxidation of the selenium centre. Previous studies have reported apparent second order rate constants for a number of oxidants (e.g. HOCl, ONOOH) with some selenium species, but these data are limited. Here we provide apparent second order rate constants for reaction of selenols (RSeH), selenides (RSeR') and diselenides (RSeSeR') with biologically-relevant oxidants (HOCl, H2O2, other peroxides) as well as overall consumption data for the excited state species singlet oxygen (1O2). Selenols show very high reactivity with HOCl and 1O2, with rate constants > 108 M-1 s-1, whilst selenides and diselenides typically react with rate constants one- (selenides) or two- (diselenides) orders of magnitude slower. Rate constants for reaction of diselenides with H2O2 and other hydroperoxides are much slower, with k for H2O2 being <1 M-1 s-1, and for amino acid and peptide hydroperoxides ~102 M-1 s-1. The rate constants determined for HOCl and 1O2 with these selenium species are greater than, or similar to, rate constants for amino acid side chains on proteins, including the corresponding sulfur-centered species (Cys and Met), suggesting that selenium containing compounds may be effective oxidant scavengers. Some of these reactions may be catalytic in nature due to ready recycling of the oxidized selenium species. These data may aid the development of highly efficacious, and catalytic, oxidant scavengers.
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Compuestos de Selenio , Selenio , Peróxido de Hidrógeno , Ácido Hipocloroso , Cinética , Oxidantes , Oxidación-ReducciónRESUMEN
For almost 50 years, attempts have been made to account for the pronounced solvent effect on the lifetime of singlet molecular oxygen, O2(a1Δg). This process is dominated by the O2(a1Δg) â O2(X3Σg-) nonradiative transition. Given the comparatively low O2(a1Δg) excitation energy of â¼7880 cm-1, existing models have been built upon a foundation of electronic-to-vibrational (e-to-v) energy transfer in which C-H and O-H stretching modes in the solvent act as the dominant energy sink. The latter accounts for large H/D solvent isotope effects on the O2(a1Δg) lifetime. However, recent experiments showing a pronounced temperature effect on the O2(a1Δg) lifetime in some solvents reveal limitations in these models. We have developed a general and computationally tenable model that accounts for both temperature and H/D solvent isotope effects on the O2(a1Δg) lifetime. A key feature of our approach is the need to strike a balance in the oxygen-solvent interaction between weak and strong coupling. In the weak coupling limit, the O2(a1Δg) â O2(X3Σg-) transition probability is determined by the overlap of vibrational wave functions, and this is the main component defining the H/D isotope effects. In the strong coupling limit, the transition probability is determined by an activated process and thus accounts for the observed temperature dependence. In addition to resolving a long-standing oxygen-dependent problem, our model may provide useful insights into a wide range of bimolecular interactions that involve e-to-v energy transfer.
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Mr4511 from Methylobacterium radiotolerans is a 164 amino acid protein built of a flavin mononucleotide (FMN) binding, blue-light responsive LOV (Light, Oxygen, Voltage) core domain plus flanking regions. In contrast to the majority of LOV domains, Mr4511 lacks a tryptophan residue that was previously identified as a major quencher for the FMN triplet state in photosensitizers for singlet oxygen (SO) engineered from these photoreceptors. Here we show that for Mr4511 it is sufficient to only mutate the reactive cysteine responsible for the photocycle (Cys71) in the native protein to generate an efficient SO photosensitizer: both C71S and C71G variants exhibit SO quantum yields of formation, ΦΔ, around 0.2 in air-saturated solutions. Under oxygen saturated conditions, ΦΔ reaches â¼0.5 in deuterated buffer. The introduction of Trp112 in the canonical position for LOV domains dramatically lowers ΦΔ to values comparable to miniSOG, one of the early FMN binding proteins touted as a SO sensitizer. Besides its SO properties, Mr4511 is also exceedingly robust against denaturation with urea and is more photostable than free FMN.