Singlet-triplet splittings from the virial theorem and single-particle excitation energies

NASA Astrophysics Data System (ADS)

Becke, Axel D.

2018-01-01

The zeroth-order (uncorrelated) singlet-triplet energy difference in single-particle excited configurations is 2Kif, where Kif is the Coulomb self-energy of the product of the transition orbitals. Here we present a non-empirical, virial-theorem argument that the correlated singlet-triplet energy difference should be half of this, namely, Kif. This incredibly simple result gives vertical HOMO-LUMO excitation energies in small-molecule benchmarks as good as the popular TD-B3LYP time-dependent approach to excited states. For linear acenes and nonlinear polycyclic aromatic hydrocarbons, the performance is significantly better than TD-B3LYP. In addition to the virial theorem, the derivation borrows intuitive pair-density concepts from density-functional theory.

Irreducible Green's functions method for a quantum dot coupled to metallic and superconducting leads

NASA Astrophysics Data System (ADS)

Górski, Grzegorz; Kucab, Krzysztof

2017-05-01

Using irreducible Green's functions (IGF) method we analyse the Coulomb interaction dependence of the spectral functions and the transport properties of a quantum dot coupled to isotropic superconductor and metallic leads (SC-QD-N). The irreducible Green's functions method is the modification of classical equation of motion technique. The IGF scheme is based on differentiation of double-time Green's functions, both over the primary and secondary times. The IGF method allows to obtain the spectral functions for equilibrium and non-equilibrium impurity Anderson model used for SC-QD-N system. By the numerical computations, we show the change of spectral and the anomalous densities under the influence of the Coulomb interactions. The observed sign change of the anomalous spectral density can be used as the criterion of the SC singlet-Kondo singlet transition.

New photosensitizers for photodynamic therapy

PubMed Central

Abrahamse, Heidi; Hamblin, Michael R.

2016-01-01

Photodynamic therapy (PDT) was discovered more than 100 years ago, and has since become a well-studied therapy for cancer and various non-malignant diseases including infections. PDT uses photosensitizers (PSs, non-toxic dyes) that are activated by absorption of visible light to initially form the excited singlet state, followed by transition to the long-lived excited triplet state. This triplet state can undergo photochemical reactions in the presence of oxygen to form reactive oxygen species (including singlet oxygen) that can destroy cancer cells, pathogenic microbes and unwanted tissue. The dual-specificity of PDT relies on accumulation of the PS in diseased tissue and also on localized light delivery. Tetrapyrrole structures such as porphyrins, chlorins, bacteriochlorins and phthalocyanines with appropriate functionalization have been widely investigated in PDT, and several compounds have received clinical approval. Other molecular structures including the synthetic dyes classes as phenothiazinium, squaraine and BODIPY (boron-dipyrromethene), transition metal complexes, and natural products such as hypericin, riboflavin and curcumin have been investigated. Targeted PDT uses PSs conjugated to antibodies, peptides, proteins and other ligands with specific cellular receptors. Nanotechnology has made a significant contribution to PDT, giving rise to approaches such as nanoparticle delivery, fullerene-based PSs, titania photocatalysis, and the use of upconverting nanoparticles to increase light penetration into tissue. Future directions include photochemical internalization, genetically encoded protein PSs, theranostics, two-photon absorption PDT, and sonodynamic therapy using ultrasound. PMID:26862179

New photosensitizers for photodynamic therapy.

PubMed

Abrahamse, Heidi; Hamblin, Michael R

2016-02-15

Photodynamic therapy (PDT) was discovered more than 100 years ago, and has since become a well-studied therapy for cancer and various non-malignant diseases including infections. PDT uses photosensitizers (PSs, non-toxic dyes) that are activated by absorption of visible light to initially form the excited singlet state, followed by transition to the long-lived excited triplet state. This triplet state can undergo photochemical reactions in the presence of oxygen to form reactive oxygen species (including singlet oxygen) that can destroy cancer cells, pathogenic microbes and unwanted tissue. The dual-specificity of PDT relies on accumulation of the PS in diseased tissue and also on localized light delivery. Tetrapyrrole structures such as porphyrins, chlorins, bacteriochlorins and phthalocyanines with appropriate functionalization have been widely investigated in PDT, and several compounds have received clinical approval. Other molecular structures including the synthetic dyes classes as phenothiazinium, squaraine and BODIPY (boron-dipyrromethene), transition metal complexes, and natural products such as hypericin, riboflavin and curcumin have been investigated. Targeted PDT uses PSs conjugated to antibodies, peptides, proteins and other ligands with specific cellular receptors. Nanotechnology has made a significant contribution to PDT, giving rise to approaches such as nanoparticle delivery, fullerene-based PSs, titania photocatalysis, and the use of upconverting nanoparticles to increase light penetration into tissue. Future directions include photochemical internalization, genetically encoded protein PSs, theranostics, two-photon absorption PDT, and sonodynamic therapy using ultrasound. © 2016 Authors; published by Portland Press Limited.

Non-resonant collider signatures of a singlet-driven electroweak phase transition

NASA Astrophysics Data System (ADS)

Chen, Chien-Yi; Kozaczuk, Jonathan; Lewis, Ian M.

2017-08-01

We analyze the collider signatures of the real singlet extension of the Standard Model in regions consistent with a strong first-order electroweak phase transition and a singlet-like scalar heavier than the Standard Model-like Higgs. A definitive correlation exists between the strength of the phase transition and the trilinear coupling of the Higgs to two singlet-like scalars, and hence between the phase transition and non-resonant scalar pair production involving the singlet at colliders. We study the prospects for observing these processes at the LHC and a future 100 TeV pp collider, focusing particularly on double singlet production. We also discuss correlations between the strength of the electroweak phase transition and other observables at hadron and future lepton colliders. Searches for non-resonant singlet-like scalar pair production at 100 TeV would provide a sensitive probe of the electroweak phase transition in this model, complementing resonant di-Higgs searches and precision measurements. Our study illustrates a strategy for systematically exploring the phenomenologically viable parameter space of this model, which we hope will be useful for future work.

Non-resonant collider signatures of a singlet-driven electroweak phase transition

DOE PAGES

Chen, Chien-Yi; Kozaczuk, Jonathan; Lewis, Ian M.

2017-08-22

We analyze the collider signatures of the real singlet extension of the Standard Model in regions consistent with a strong first-order electroweak phase transition and a singlet-like scalar heavier than the Standard Model-like Higgs. A definitive correlation exists between the strength of the phase transition and the trilinear coupling of the Higgs to two singlet-like scalars, and hence between the phase transition and non-resonant scalar pair production involving the singlet at colliders. We study the prospects for observing these processes at the LHC and a future 100 TeV pp collider, focusing particularly on double singlet production. We also discuss correlationsmore » between the strength of the electroweak phase transition and other observables at hadron and future lepton colliders. Searches for non-resonant singlet-like scalar pair production at 100 TeV would provide a sensitive probe of the electroweak phase transition in this model, complementing resonant di-Higgs searches and precision measurements. Our study illustrates a strategy for systematically exploring the phenomenologically viable parameter space of this model, which we hope will be useful for future work.« less

Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

PubMed Central

Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

PubMed

Morales, Javier; Günther, Germán; Zanocco, Antonio L; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

Copper phthalocyanine-based CMPs with various internal structures and functionalities.

PubMed

Ding, Xuesong; Han, Bao-Hang

2015-08-18

Several kinds of copper phthalocyanine-based conjugated microporous polymers have been synthesized, which present enhanced long-wavelength photon absorption capability and high efficiency for singlet oxygen generation under low energy light irradiation. This strategy opens a facile avenue towards expanding the scope of phthalocyanine-based porous materials with various internal structures and functionalities.

Singlet exciton fission photovoltaics.

PubMed

Lee, Jiye; Jadhav, Priya; Reusswig, Philip D; Yost, Shane R; Thompson, Nicholas J; Congreve, Daniel N; Hontz, Eric; Van Voorhis, Troy; Baldo, Marc A

2013-06-18

Singlet exciton fission, a process that generates two excitons from a single photon, is perhaps the most efficient of the various multiexciton-generation processes studied to date, offering the potential to increase the efficiency of solar devices. But its unique characteristic, splitting a photogenerated singlet exciton into two dark triplet states, means that the empty absorption region between the singlet and triplet excitons must be filled by adding another material that captures low-energy photons. This has required the development of specialized device architectures. In this Account, we review work to develop devices that harness the theoretical benefits of singlet exciton fission. First, we discuss singlet fission in the archetypal material, pentacene. Pentacene-based photovoltaic devices typically show high external and internal quantum efficiencies. They have enabled researchers to characterize fission, including yield and the impact of competing loss processes, within functional devices. We review in situ probes of singlet fission that modulate the photocurrent using a magnetic field. We also summarize studies of the dissociation of triplet excitons into charge at the pentacene-buckyball (C60) donor-acceptor interface. Multiple independent measurements confirm that pentacene triplet excitons can dissociate at the C60 interface despite their relatively low energy. Because triplet excitons produced by singlet fission each have no more than half the energy of the original photoexcitation, they limit the potential open circuit voltage within a solar cell. Thus, if singlet fission is to increase the overall efficiency of a solar cell and not just double the photocurrent at the cost of halving the voltage, it is necessary to also harvest photons in the absorption gap between the singlet and triplet energies of the singlet fission material. We review two device architectures that attempt this using long-wavelength materials: a three-layer structure that uses long- and short-wavelength donors and an acceptor and a simpler, two-layer combination of a singlet-fission donor and a long-wavelength acceptor. An example of the trilayer structure is singlet fission in tetracene with copper phthalocyanine inserted at the C60 interface. The bilayer approach includes pentacene photovoltaic cells with an acceptor of infrared-absorbing lead sulfide or lead selenide nanocrystals. Lead selenide nanocrystals appear to be the most promising acceptors, exhibiting efficient triplet exciton dissociation and high power conversion efficiency. Finally, we review architectures that use singlet fission materials to sensitize other absorbers, thereby effectively converting conventional donor materials to singlet fission dyes. In these devices, photoexcitation occurs in a particular molecule and then energy is transferred to a singlet fission dye where the fission occurs. For example, rubrene inserted between a donor and an acceptor decouples the ability to perform singlet fission from other major photovoltaic properties such as light absorption.

Structural and functional imaging for vascular targeted photodynamic therapy

NASA Astrophysics Data System (ADS)

Li, Buhong; Gu, Ying; Wilson, Brian C.

2017-02-01

Vascular targeted photodynamic therapy (V-PDT) has been widely used for the prevention or treatment of vascular-related diseases, such as localized prostate cancer, wet age-related macular degeneration, port wine stains, esophageal varices and bleeding gastrointestinal mucosal lesions. In this study, the fundamental mechanisms of vascular responses during and after V-PDT will be introduced. Based on the V-PDT treatment of blood vessels in dorsal skinfold window chamber model, the structural and functional imaging, which including white light microscopy, laser speckle imaging, singlet oxygen luminescence imaging, and fluorescence imaging for evaluating vascular damage will be presented, respectively. The results indicate that vessel constriction and blood flow dynamics could be considered as the crucial biomarkers for quantitative evaluation of vascular damage. In addition, future perspectives of non-invasive optical imaging for evaluating vascular damage of V-PDT will be discussed.

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

DOE PAGES

Zhao, Z. Y.; Calder, S.; Aczel, A. A.; ...

2016-04-25

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Z. Y.; Calder, S.; Aczel, A. A.

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Unified model for singlet fission within a non-conjugated covalent pentacene dimer

NASA Astrophysics Data System (ADS)

Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin; Phelan, Brian T.; Krzyaniak, Matthew D.; Reddy, S. Rajagopala; Coto, Pedro B.; Horwitz, Noah E.; Young, Ryan M.; White, Fraser J.; Hampel, Frank; Clark, Timothy; Thoss, Michael; Tykwinski, Rik R.; Wasielewski, Michael R.; Guldi, Dirk M.

2017-05-01

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron-hole pairs, leading to a predicted ~50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.

Unified model for singlet fission within a non-conjugated covalent pentacene dimer.

PubMed

Basel, Bettina S; Zirzlmeier, Johannes; Hetzer, Constantin; Phelan, Brian T; Krzyaniak, Matthew D; Reddy, S Rajagopala; Coto, Pedro B; Horwitz, Noah E; Young, Ryan M; White, Fraser J; Hampel, Frank; Clark, Timothy; Thoss, Michael; Tykwinski, Rik R; Wasielewski, Michael R; Guldi, Dirk M

2017-05-18

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron-hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.

DFT and ab initio study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manaa, M.R.; Fried, L.E.

1998-11-26

The fully optimized potential energy curves for the unimolecular decomposition of the lowest singlet and triplet states of nitromethane through the C-NO{sub 2} bond dissociation pathway are calculated using various DFT and high-level ab initio electronic structure methods. The authors perform gradient corrected density functional theory (DFT) and multiconfiguration self-consistent field (MCSCF) to conclusively demonstrate that the triplet state of nitromethane is bound. The adiabatic curve of this state exhibits a 33 kcal/mol energy barrier as determined at the MCSCF level. DFT methods locate this barrier at a shorter C-N bond distance with 12--16 kcal/mol lower energy than does MCSCF.more » In addition to MCSCF and DFT, quadratic configuration interactions with single and double substitutions (QCISD) calculations are also performed for the singlet curve. The potential energy profiles of this state predicted by FT methods based on Becke`s 1988 exchange functional differ by as much as 17 kcal/mol from the predictions of MCSCF and QCISD in the vicinity of the equilibrium structure. The computational methods predict bond dissociation energies 5--9 kcal/mol lower than the experimental value. DFT techniques based on Becke`s 3-parameter exchange functional show the best overall agreement with the higher level methods.« less

Model studies of hydrogen atom addition and abstraction processes involving ortho-, meta-, and para-benzynes.

PubMed

Clark, A E; Davidson, E R

2001-10-31

H-atom addition and abstraction processes involving ortho-, meta-, and para-benzyne have been investigated by multiconfigurational self-consistent field methods. The H(A) + H(B)...H(C) reaction (where r(BC) is adjusted to mimic the appropriate singlet-triplet energy gap) is shown to effectively model H-atom addition to benzyne. The doublet multiconfiguration wave functions are shown to mix the "singlet" and "triplet" valence bond structures of H(B)...H(C) along the reaction coordinate; however, the extent of mixing is dependent on the singlet-triplet energy gap (DeltaE(ST)) of the H(B)...H(C) diradical. Early in the reaction, the ground-state wave function is essentially the "singlet" VB function, yet it gains significant "triplet" VB character along the reaction coordinate that allows H(A)-H(B) bond formation. Conversely, the wave function of the first excited state is predominantly the "triplet" VB configuration early in the reaction coordinate, but gains "singlet" VB character when the H-atom is close to a radical center. As a result, the potential energy surface (PES) for H-atom addition to triplet H(B)...H(C) diradical is repulsive! The H3 model predicts, in agreement with the actual calculations on benzyne, that the singlet diradical electrons are not coupled strongly enough to give rise to an activation barrier associated with C-H bond formation. Moreover, this model predicts that the PES for H-atom addition to triplet benzyne will be characterized by a repulsive curve early in the reaction coordinate, followed by a potential avoided crossing with the (pi)1(sigma*)1 state of the phenyl radical. In contrast to H-atom addition, large activation barriers characterize the abstraction process in both the singlet ground state and first triplet state. In the ground state, this barrier results from the weakly avoided crossing of the dominant VB configurations in the ground-state singlet (S0) and first excited singlet (S1) because of the large energy gap between S0 and S1 early in the reaction coordinate. Because the S1 state is best described as the combination of the triplet X-H bond and the triplet H(B)...H(C) spin couplings, the activation barrier along the S0 abstraction PES will have much less dependence on the DeltaE(ST) of H(B)...H(C) than previously speculated. For similar reasons, the T1 potential surface is quite comparable to the S0 PES.

Phytoalexin Phenalenone Derivatives Inactivate Mosquito Larvae and Root-knot Nematode as Type-II Photosensitizer

NASA Astrophysics Data System (ADS)

Song, Runjiang; Feng, Yian; Wang, Donghui; Xu, Zhiping; Li, Zhong; Shao, Xusheng

2017-02-01

Phytoalexins phenalenones (PNs) are phytochemicals biosynthesized inside the plant in responsive to exterior threat. PNs are excellent type-II photosensitizers, which efficiently produce singlet oxygen upon light irradiation. Based on the core functional structure of PNs, novel PN derivatives were synthesized here and their singlet oxygen generating abilities and their phototoxicity were evaluated. At the presence of light, these PNs have photoinduced toxicity towards Aedes albopictus larvae and nematode Meloidogyne incognita, while the activity lost in the dark. The obvious tissue damage was observed on the treated mosquito larvae and nematode due to the generation of singlet oxygen. Our results revealed the potential of phenalenones as photoactivated agents for mosquito and root-knot nematode management together with light.

Unified model for singlet fission within a non-conjugated covalent pentacene dimer

DOE PAGES

Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin; ...

2017-05-18

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted B50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state thatmore » precedes formation of the pentacene triplet excitons. In conclusion, using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.« less

Unified model for singlet fission within a non-conjugated covalent pentacene dimer

PubMed Central

Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin; Phelan, Brian T.; Krzyaniak, Matthew D.; Reddy, S. Rajagopala; Coto, Pedro B.; Horwitz, Noah E.; Young, Ryan M.; White, Fraser J.; Hampel, Frank; Clark, Timothy; Thoss, Michael; Tykwinski, Rik R.; Wasielewski, Michael R.; Guldi, Dirk M.

2017-01-01

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures. PMID:28516916

New singlet oxygen donors based on naphthalenes: synthesis, physical chemical data, and improved stability.

PubMed

Klaper, Matthias; Linker, Torsten

2015-06-01

Singlet oxygen donors are of current interest for medical applications, but suffer from a short half-life leading to low singlet oxygen yields and problems with storage. We have synthesized more than 25 new singlet oxygen donors based on differently substituted naphthalenes in only a few steps. The influence of functional groups on the reaction rate of the photooxygenations, thermolysis, half-life, and singlet oxygen yield has been thoroughly studied. We determined various thermodynamic data and compared them with density functional calculations. Interestingly, remarkable stabilities of functional groups during the photooxygenations and stabilizing effects for some endoperoxides during the thermolysis have been found. Furthermore, we give evidence for a partly concerted and partly stepwise thermolysis mechanism leading to singlet and triplet oxygen, respectively. Our results might be interesting for "dark oxygenations" and future applications in medicine. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correct definition of color singlet P-wave non-perturbative matrix element of heavy quarkonium production

NASA Astrophysics Data System (ADS)

Nayak, Gouranga C.

2017-09-01

Recently we have proved factorization of infrared divergences in NRQCD S-wave heavy quarkonium production at high energy colliders at all orders in coupling constant. One of the problem which still exists in the higher order pQCD calculation of color singlet P-wave heavy quarkonium production/anihillation is the appearance of noncanceling infrared divergences due to real soft gluons exchange, although no such infrared divergences are present in the color singlet S-wave heavy quarkonium. In this paper we find that since the non-perturbative matrix element of the color singlet P-wave heavy quarkonium production contains derivative operators, the gauge links are necessary to make it gauge invariant and be consistent with the factorization of such non-canceling infrared divergences at all orders in coupling constant.

Helicity evolution at small x : Flavor singlet and nonsinglet observables

DOE PAGES

Kovchegov, Yuri V.; Pitonyak, Daniel; Sievert, Matthew D.

2017-01-30

We extend our earlier results for the quark helicity evolution at small x to derive the small-x asymptotics of the flavor singlet and flavor nonsinglet quark helicity TMDs and PDFs and of the g 1 structure function. In the flavor singlet case we rederive the evolution equations obtained in our previous paper on the subject, performing additional cross-checks of our results. In the flavor nonsinglet case we construct new small-x evolution equations by employing the large-N c limit. Here, all evolution equations resum double-logarithmic powers of α sln 2(1/x) in the polarization-dependent evolution along with the single-logarithmic powers of αmore » sln(1/x) in the unpolarized evolution which includes saturation effects.« less

Helicity evolution at small x : Flavor singlet and nonsinglet observables

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovchegov, Yuri V.; Pitonyak, Daniel; Sievert, Matthew D.

We extend our earlier results for the quark helicity evolution at small x to derive the small-x asymptotics of the flavor singlet and flavor nonsinglet quark helicity TMDs and PDFs and of the g 1 structure function. In the flavor singlet case we rederive the evolution equations obtained in our previous paper on the subject, performing additional cross-checks of our results. In the flavor nonsinglet case we construct new small-x evolution equations by employing the large-N c limit. Here, all evolution equations resum double-logarithmic powers of α sln 2(1/x) in the polarization-dependent evolution along with the single-logarithmic powers of αmore » sln(1/x) in the unpolarized evolution which includes saturation effects.« less

A transferable model for singlet-fission kinetics.

PubMed

Yost, Shane R; Lee, Jiye; Wilson, Mark W B; Wu, Tony; McMahon, David P; Parkhurst, Rebecca R; Thompson, Nicholas J; Congreve, Daniel N; Rao, Akshay; Johnson, Kerr; Sfeir, Matthew Y; Bawendi, Moungi G; Swager, Timothy M; Friend, Richard H; Baldo, Marc A; Van Voorhis, Troy

2014-06-01

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications.

Photosensitization of Intact Heart Mitochondria by the Phthalocyanine Pc 4: Correlation of Structural and Functional Deficits with Cytochrome c Release

PubMed Central

Kim, Junhwan; Fujioka, Hisashi; Oleinick, Nancy L.; Anderson, Vernon E.

2010-01-01

Singlet oxygen is produced by absorption of red light by the phthalocyanine dye, Pc 4, followed by energy transfer to dissolved triplet oxygen. Mitochondria pre-incubated with Pc 4 were illuminated by red light and the damage to mitochondrial structure and function by the generated singlet oxygen was studied. At early illumination times (3–5 min. of red light exposure), state 3 respiration was inhibited (50%) while state 4 activity increased, resulting in effectively complete uncoupling. Individual complex activities were measured and only complex IV activity was significantly reduced and exhibited a dose response while the activities of electron transport complexes I, II and III were not significantly affected. Cyt c release was an increasing function of irradiation time with 30% being released following 5 min. of illumination. Mitochondrial expansion along with changes in the structure of the cristae were observed by transmission electron microscopy following 5 min. of irradiation with an increase of large vacuoles and membrane rupture occurring following more extensive exposures. PMID:20510354

Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

PubMed

Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

2010-11-04

Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

Exact exchange-correlation potentials of singlet two-electron systems

NASA Astrophysics Data System (ADS)

Ryabinkin, Ilya G.; Ospadov, Egor; Staroverov, Viktor N.

2017-10-01

We suggest a non-iterative analytic method for constructing the exchange-correlation potential, v XC ( r ) , of any singlet ground-state two-electron system. The method is based on a convenient formula for v XC ( r ) in terms of quantities determined only by the system's electronic wave function, exact or approximate, and is essentially different from the Kohn-Sham inversion technique. When applied to Gaussian-basis-set wave functions, the method yields finite-basis-set approximations to the corresponding basis-set-limit v XC ( r ) , whereas the Kohn-Sham inversion produces physically inappropriate (oscillatory and divergent) potentials. The effectiveness of the procedure is demonstrated by computing accurate exchange-correlation potentials of several two-electron systems (helium isoelectronic series, H2, H3 + ) using common ab initio methods and Gaussian basis sets.

A density-functional-theory study of biradicals from benzene to hexacene

NASA Astrophysics Data System (ADS)

Kim, Hyun-Jung; Wang, Xingyong; Ma, Jing; Cho, Jun-Hyung

2011-11-01

The singlet-triplet energy gap of biradicals created in benzene and polyacenes is investigated by density-functional-theory calculations. For the biradicals in benzene, naphthalene, anthracene, tetracene, pentacene, and hexacene, we find that the singlet state is energetically favored over the triplet state by 189, 191, 184, 199, 218, and 244 meV, respectively. The monotonous increase of the singlet-triplet energy gap from anthracene to hexacene is attributed to the enhanced stability of the singlet state for longer polyacenes. Our analysis shows that the spin density of the singlet state is delocalized over all benzene rings, but such a spin delocalization is not present for the triplet state.

Singlet Orbital Ordering in Bilayer Sr_{3}Cr_{2}O_{7}.

PubMed

Jeanneau, Justin; Toulemonde, Pierre; Remenyi, Gyorgy; Sulpice, André; Colin, Claire; Nassif, Vivian; Suard, Emmanuelle; Salas Colera, Eduardo; Castro, Germán R; Gay, Frederic; Urdaniz, Corina; Weht, Ruben; Fevrier, Clement; Ralko, Arnaud; Lacroix, Claudine; Aligia, Armando A; Núñez-Regueiro, Manuel

2017-05-19

We perform an extensive study of Sr_{3}Cr_{2}O_{7}, the n=2 member of the Ruddlesden-Popper Sr_{n+1}Cr_{n}O_{3n+1} system. An antiferromagnetic ordering is clearly visible in the magnetization and the specific heat, which yields a huge transition entropy, Rln(6). By neutron diffraction as a function of temperature we have determined the antiferromagnetic structure that coincides with the one obtained from density functional theory calculations. It is accompanied by anomalous asymmetric distortions of the CrO_{6} octahedra. Strong coupling and Lanczos calculations on a derived Kugel-Khomskii Hamiltonian yield a simultaneous orbital and moment ordering. Our results favor an exotic ordered phase of orbital singlets not originated by frustration.

Gas response behaviour and photochemistry of borondiketonate in acrylic polymer matrices for sensing applications.

PubMed

Arias Espinoza, Juan Diego; Sazhnikov, Viacheslav; Smits, Edsger C P; Ionov, Dmirity; Kononevich, Yuriy; Yakimets, Iryna; Alfimov, Mikael; Schoo, Herman F M

2014-11-01

The fluorescent spectra in combination with gas response behavior of acrylic polymers doped with dibenzoyl(methanato)boron difluoride (DBMBF2) were studied by fluorescence spectroscopy and time-resolved fluorescence lifetime. The role of acrylic matrix polarity upon the fluorescence spectra and fluorescence lifetime was analyzed. Changes in emission of the dye doped polymers under exposure to toluene, n-hexane and ethanol were monitored. The fluorescence lifetimes were measured for the singlet excited state as well as the exciplex formed between DBMBF2 and toluene. A reduction of the transition energy to the first singlet-excited state in the four polymers was observed, compared to solution. Reversible exciplex formation, viz. a red shifted fluorescence emission was perceived when exposing the polymers to toluene, while for hexane and ethanol only reversible reduction of the fluorescence occurred. Longer singlet and shorter exciplex lifetimes were observed for non-polar matrixes. The latter mechanism is explained in function of the lower charge transfer character of the exciplex in non-polar matrixes. Additionally, the quantum yield of the dye in the polymer matrix increased almost seventh-fold compared to values for solution.

Cholecystokinin 1 Receptor - A Unique G Protein-Coupled Receptor Activated by Singlet Oxygen (GPCR-ABSO).

PubMed

Jiang, Hong Ning; Li, Yuan; Jiang, Wen Yi; Cui, Zong Jie

2018-01-01

Plasma membrane-delimited generation of singlet oxygen by photodynamic action with photosensitizer sulfonated aluminum phthalocyanine (SALPC) activates cholecystokinin 1 receptor (CCK1R) in pancreatic acini. Whether CCK1R retains such photooxidative singlet oxygen activation properties in other environments is not known. Genetically encoded protein photosensitizers KillerRed or mini singlet oxygen generator (miniSOG) were expressed in pancreatic acinar tumor cell line AR4-2J, CCK1R, KillerRed or miniSOG were expressed in HEK293 or CHO-K1 cells. Cold light irradiation (87 mW⋅cm -2 ) was applied to photosensitizer-expressing cells to examine photodynamic activation of CCK1R by Fura-2 fluorescent calcium imaging. When CCK1R was transduced into HEK293 cells which lack endogenous CCK1R, photodynamic action with SALPC was found to activate CCK1R in CCK1R-HEK293 cells. When KillerRed or miniSOG were transduced into AR4-2J which expresses endogenous CCK1R, KillerRed or miniSOG photodynamic action at the plasma membrane also activated CCK1R. When fused KillerRed-CCK1R was transduced into CHO-K1 cells, light irradiation activated the fused CCK1R leading to calcium oscillations. Therefore KillerRed either expressed independently, or fused with CCK1R can both activate CCK1R photodynamically. It is concluded that photodynamic singlet oxygen activation is an intrinsic property of CCK1R, independent of photosensitizer used, or CCK1R-expressing cell types. Photodynamic singlet oxygen CCK1R activation after transduction of genetically encoded photosensitizer in situ may provide a convenient way to verify intrinsic physiological functions of CCK1R in multiple CCK1R-expressing cells and tissues, or to actuate CCK1R function in CCK1R-expressing and non-expressing cell types after transduction with fused KillerRed-CCK1R.

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission.

PubMed

Hart, Stephanie M; Silva, W Ruchira; Frontiera, Renee R

2018-02-07

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

Characterization of Photofrin photobleaching for singlet oxygen dose estimation during photodynamic therapy of MLL cells in vitro

NASA Astrophysics Data System (ADS)

Dysart, Jonathan S.; Patterson, Michael S.

2005-06-01

A singlet oxygen dose model is developed for PDT with Photofrin. The model is based on photosensitizer photobleaching kinetics, and incorporates both singlet oxygen and non-singlet oxygen mediated bleaching mechanisms. To test our model, in vitro experiments were performed in which MatLyLu (MLL) cells were incubated in Photofrin and then irradiated with 532 nm light. Photofrin fluorescence was monitored during treatment and, at selected fluence levels, cell viability was determined using a colony formation assay. Cell survival correlated well to calculated singlet oxygen dose, independent of initial Photofrin concentration or oxygenation. About 2 × 108 molecules of singlet oxygen per cell were required to reduce the surviving fraction by 1/e. Analysis of the photobleaching kinetics suggests that the lifetime of singlet oxygen in cells is 0.048 ± 0.005 µs. The generation of fluorescent photoproducts was not a result of singlet oxygen reactions exclusively, and therefore did not yield additional information to aid in quantifying singlet oxygen dose.

DOE Office of Scientific and Technical Information (OSTI.GOV)

König, Johannes; Merle, Alexander; Totzauer, Maximilian

We investigate the early Universe production of sterile neutrino Dark Matter by the decays of singlet scalars. All previous studies applied simplifying assumptions and/or studied the process only on the level of number densities, which makes it impossible to give statements about cosmic structure formation. We overcome these issues by dropping all simplifying assumptions (except for one we showed earlier to work perfectly) and by computing the full course of Dark Matter production on the level of non-thermal momentum distribution functions. We are thus in the position to study a broad range of aspects of the resulting settings and applymore » a broad set of bounds in a reliable manner. We have a particular focus on how to incorporate bounds from structure formation on the level of the linear power spectrum, since the simplistic estimate using the free-streaming horizon clearly fails for highly non-thermal distributions. Our work comprises the most detailed and comprehensive study of sterile neutrino Dark Matter production by scalar decays presented so far.« less

Fingerprints of heavy scales in electroweak effective Lagrangians

NASA Astrophysics Data System (ADS)

Pich, Antonio; Rosell, Ignasi; Santos, Joaquín; Sanz-Cillero, Juan José

2017-04-01

The couplings of the electroweak effective theory contain information on the heavy-mass scales which are no-longer present in the low-energy Lagrangian. We build a general effective Lagrangian, implementing the electroweak chiral symmetry breaking SU(2) L ⊗ SU(2) R → SU(2) L+ R , which couples the known particle fields to heavier states with bosonic quantum numbers J P = 0± and 1±. We consider colour-singlet heavy fields that are in singlet or triplet representations of the electroweak group. Integrating out these heavy scales, we analyze the pattern of low-energy couplings among the light fields which are generated by the massive states. We adopt a generic non-linear realization of the electroweak symmetry breaking with a singlet Higgs, without making any assumption about its possible doublet structure. Special attention is given to the different possible descriptions of massive spin-1 fields and the differences arising from naive implementations of these formalisms, showing their full equivalence once a proper short-distance behaviour is required.

Effects of an additional conduction band on the singlet-antiferromagnet competition in the periodic Anderson model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Wenjian; Scalettar, Richard T.; Huang, Edwin W.

The competition between antiferromagnetic (AF) order and singlet formation is a central phenomenon of the Kondo and periodic Anderson Hamiltonians and of the heavy fermion materials they describe. In this paper, we explore the effects of an additional conduction band on magnetism in these models, and, specifically, on changes in the AF-singlet quantum critical point (QCP) and the one particle and spin spectral functions. To understand the magnetic phase transition qualitatively, we first carry out a self-consistent mean field theory (MFT). The basic conclusion is that, at half filling, the coupling to the additional band stabilizes the AF phase tomore » larger f d hybridization V in the PAM. We also explore the possibility of competing ferromagnetic phases when this conduction band is doped away from half filling. Here, we next employ quantum Monte Carlo (QMC) which, in combination with finite size scaling, allows us to evaluate the position of the QCP using an exact treatment of the interactions. This approach confirms the stabilization of AF order, which occurs through an enhancement of the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction. QMC results for the spectral function A (q,ω) and dynamic spin structure factor χ (q,ω) yield additional insight into the AF-singlet competition and the low temperature phases.« less

Effects of an additional conduction band on the singlet-antiferromagnet competition in the periodic Anderson model

DOE PAGES

Hu, Wenjian; Scalettar, Richard T.; Huang, Edwin W.; ...

2017-06-12

The competition between antiferromagnetic (AF) order and singlet formation is a central phenomenon of the Kondo and periodic Anderson Hamiltonians and of the heavy fermion materials they describe. In this paper, we explore the effects of an additional conduction band on magnetism in these models, and, specifically, on changes in the AF-singlet quantum critical point (QCP) and the one particle and spin spectral functions. To understand the magnetic phase transition qualitatively, we first carry out a self-consistent mean field theory (MFT). The basic conclusion is that, at half filling, the coupling to the additional band stabilizes the AF phase tomore » larger f d hybridization V in the PAM. We also explore the possibility of competing ferromagnetic phases when this conduction band is doped away from half filling. Here, we next employ quantum Monte Carlo (QMC) which, in combination with finite size scaling, allows us to evaluate the position of the QCP using an exact treatment of the interactions. This approach confirms the stabilization of AF order, which occurs through an enhancement of the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction. QMC results for the spectral function A (q,ω) and dynamic spin structure factor χ (q,ω) yield additional insight into the AF-singlet competition and the low temperature phases.« less

Light- and singlet oxygen-mediated antifungal activity of phenylphenalenone phytoalexins.

PubMed

Lazzaro, Alejandra; Corominas, Montserrat; Martí, Cristina; Flors, Cristina; Izquierdo, Laura R; Grillo, Teresa A; Luis, Javier G; Nonell, Santi

2004-07-01

The light-induced singlet oxygen production and antifungal activity of phenylphenalenone phytoalexins isolated from infected banana plants (Musa acuminata) are reported. Upon absorption of light energy all studied phenylphenalenones sensitise the production of singlet oxygen in polar and non-polar media. Antifungal activity of these compounds towards Fusarium oxysporum is enhanced in the presence of light. These results, together with the correlation of IC50 values under illumination with the quantum yield of singlet oxygen production and the enhancing effect of D2O on the antifungal activity, suggest the intermediacy of singlet oxygen produced by electronic excitation of the phenylphenalenone phytoalexins.

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

2017-03-01

Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life, and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

Thermal transport in topological-insulator-based superconducting hybrid structures with mixed singlet and triplet pairing states.

PubMed

Li, Hai; Zhao, Yuan Yuan

2017-11-22

In the framework of the Bogoliubov-de Gennes equation, we investigate the thermal transport properties in topological-insulator-based superconducting hybrid structures with mixed spin-singlet and spin-triplet pairing states, and emphasize the different manifestations of the spin-singlet and spin-triplet pairing states in the thermal transport signatures. It is revealed that the temperature-dependent differential thermal conductance strongly depends on the components of the pairing state, and the negative differential thermal conductance only occurs in the spin-singlet pairing state dominated regime. It is also found that the thermal conductance is profoundly sensitive to the components of the pairing state. In the spin-singlet pairing state controlled regime, the thermal conductance obviously oscillates with the phase difference and junction length. With increasing the proportion of the spin-triplet pairing state, the oscillating characteristic of the thermal conductance fades out distinctly. These results suggest an alternative route for distinguishing the components of pairing states in topological-insulator-based superconducting hybrid structures.

Hund's Multiplicity Rule Revisited

ERIC Educational Resources Information Center

Rioux, Frank

2007-01-01

The plausible and frequently used explanation of the singlet and triplet wave functions for a two-electron system is presented. Its findings reveal that the antisymmetric triplet spatial wave function keeps electrons apart, while the symmetric singlet spatial wave function permits electrons to be close together.

Origins of Singlet Fission in Solid Pentacene from an ab initio Green's Function Approach

NASA Astrophysics Data System (ADS)

Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

2017-12-01

We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a G W plus Bethe-Salpeter equation approach, we calculate the exciton-biexciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two noninteracting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay process from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 30-70 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. Our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids.

Novel fully-BODIPY functionalized cyclotetraphosphazene photosensitizers having high singlet oxygen quantum yields

NASA Astrophysics Data System (ADS)

Şenkuytu, Elif; Eçik, Esra Tanrıverdi

2017-07-01

Novel fully-BODIPY functionalized dendrimeric cyclotetraphosphazenes (FBCP 1 and 2) have been synthesized and characterized by 1H, 13C and 31P NMR spectroscopies. The photophysical and photochemical properties of FBCP 1 and 2 are investigated in dichloromethane solution. The effectiveness of singlet oxygen generation was measured for FBCP 1 and 2 by UV-Vis spectra monitoring of the solution of 1,3-diphenylisobenzofuran (DPBF), which is a well-known trapping molecule used in detection of singlet oxygen. FBCP 1 and 2 show high molar extinction coefficients in the NIR region, good singlet oxygen quantum yields and appropriate photo degradation. The data presented in the work indicate that the dendrimeric cyclotetraphosphazenes are effective singlet oxygen photosensitizers that might be used for various areas of applications such as photodynamic therapy and photocatalysis.

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Two Birds with One Stone: Tailoring Singlet Fission for Both Triplet Yield and Exciton Diffusion Length

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Tong; Wan, Yan; Guo, Zhi

2016-06-27

By direct imaging of singlet and triplet populations with ultrafast microscopy, it is shown that the triplet diffusion length and singlet fission yield can be simultaneously optimized for tetracene and its derivatives, making them ideal structures for application in bilayer solar cells.

Singlet Fission Involves an Interplay between Energetic Driving Force and Electronic Coupling in Perylenediimide Films

DOE PAGES

Le, Aaron K.; Bender, Jon A.; Arias, Dylan H.; ...

2017-12-14

Due to its ability to offset thermalization losses in photoharvesting systems, singlet fission has become a topic of research interest. During singlet fission, a high energy spin-singlet state in an organic semiconductor divides its energy to form two lower energy spin-triplet excitations on neighboring chromophores. While key insights into mechanisms leading to singlet fission have been gained recently, developing photostable compounds that undergo quantitative singlet fission remains a key challenge. In this report, we explore triplet exciton production via singlet fission in films of perylenediimides, a class of compounds with a long history of use as industrial dyes and pigmentsmore » due to their photostability. As singlet fission necessitates electron transfer between neighboring molecules, its rate and yield depend sensitively on their local arrangement. Here, by adding different functional groups at their imide positions, we control how perylenediimides pack in the solid state.« less

Singlet Fission Involves an Interplay between Energetic Driving Force and Electronic Coupling in Perylenediimide Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Le, Aaron K.; Bender, Jon A.; Arias, Dylan H.

Due to its ability to offset thermalization losses in photoharvesting systems, singlet fission has become a topic of research interest. During singlet fission, a high energy spin-singlet state in an organic semiconductor divides its energy to form two lower energy spin-triplet excitations on neighboring chromophores. While key insights into mechanisms leading to singlet fission have been gained recently, developing photostable compounds that undergo quantitative singlet fission remains a key challenge. In this report, we explore triplet exciton production via singlet fission in films of perylenediimides, a class of compounds with a long history of use as industrial dyes and pigmentsmore » due to their photostability. As singlet fission necessitates electron transfer between neighboring molecules, its rate and yield depend sensitively on their local arrangement. Here, by adding different functional groups at their imide positions, we control how perylenediimides pack in the solid state.« less

First-Principle Characterization for Singlet Fission Couplings.

PubMed

Yang, Chou-Hsun; Hsu, Chao-Ping

2015-05-21

The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly.

Relativistic potential energy surfaces of initial oxidations of Si(100) by atomic oxygen: The importance of surface dimer triplet state

NASA Astrophysics Data System (ADS)

Kim, Tae-Rae; Shin, Seokmin; Choi, Cheol Ho

2012-06-01

The non-relativistic and relativistic potential energy surfaces (PESs) of the symmetric and asymmetric reaction paths of Si(100)-2×1 oxidations by atomic oxygen were theoretically explored. Although only the singlet PES turned out to exist as a major channel leading to "on-dimer" product, both the singlet and triplet PESs leading to "on-top" products are attractive. The singlet PESs leading to the two surface products were found to be the singlet combinations (open-shell singlet) of the low-lying triplet state of surface silicon dimer and the ground 3P state of atomic oxygen. The triplet state of the "on-top" product can also be formed by the ground singlet state of the surface silicon dimer and the same 3P oxygen. The attractive singlet PESs leading to the "on-dimer" and "on-top" products made neither the intersystem crossings from triplet to singlet PES nor high energy 1D of atomic oxygen necessary. Rather, the low-lying triplet state of surface silicon dimer plays an important role in the initial oxidations of silicon surface.

Effect of the solvent environment on the spectroscopic properties and dynamics of the lowest excited states of carotenoids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frank, H.A.; Bautista, J.A.; Josue, J.

2000-05-11

The spectroscopic properties and dynamics of the lowest excited singlet states of peridinin, fucoxanthin, neoxanthin, uriolide acetate, spheroidene, and spheroidenone in several different solvents have been studied by steady-state absorption and fast-transient optical spectroscopic techniques. Peridinin, fucoxanthin, uriolide acetate, and spheroidenone, which contain carbonyl functional groups in conjugation with the carbon-carbon {pi}-electron system, display broader absorption spectral features and are affected more by the solvent environment than neoxanthin and spheroidene, which do not contain carbonyl functional groups. The possible sources of the spectral broadening are explored by examining the absorption spectra at 77 K in glassy solvents. Also, carotenoids whichmore » contain carbonyls have complex transient absorption spectra and show a pronounced dependence of the excited singlet state lifetime on the solvent environment. It is postulated that these effects are related to the presence of an intramolecular charge transfer state strongly coupled to the S{sub 1} (2{sup 1}A{sub g}) excited singlet state. Structural variations in the series of carotenoids studied here make it possible to focus on the general molecular features that control the spectroscopic and dynamic properties of carotenoids.« less

Photo-oxidation of ergosterol: indirect detection of antioxidants photosensitizers or quenchers of singlet oxygen.

PubMed

Lagunes, Irene; Trigos, Ángel

2015-04-01

Consumption of antioxidant supplements is associated to prevention of several diseases. However, recent studies suggest that antioxidants, besides scavenge free radicals could lead development of tumors. Due to conflicting reports on the antioxidant benefits, the capacity to photosensitize the generation of singlet oxygen of seven natural antioxidants was evaluated through photo-oxidation of ergosterol which proved to be an efficient method of indirect detection of singlet oxygen. Our results showed that curcumin, resveratrol and quercetin have pro-oxidant activity due they act as photosensitizers in generation of singlet oxygen. In addition, we observed that genistein, naringenin, β-carotene and gallic acid besides their antioxidant activity against ROS radicals, are capable of quenching ROS non-radicals as singlet oxygen. Finally, our results allow us to propose a new approach in classification of natural antioxidants scavengers of free radicals, based on their activity as quenchers of singlet oxygen or as photosensitizers in singlet oxygen generation. Copyright © 2015. Published by Elsevier B.V.

A spin exchange model for singlet fission

NASA Astrophysics Data System (ADS)

Yago, Tomoaki; Wakasa, Masanobu

2018-03-01

Singlet fission has been analyzed with the Dexter model in which electron exchange occurs between chromophores, conserving the spin for each electron. In the present study, we propose a spin exchange model for singlet fission. In the spin exchange model, spins are exchanged by the exchange interaction between two electrons. Our analysis with simple spin functions demonstrates that singlet fission is possible by spin exchange. A necessary condition for spin exchange is a variation in exchange interactions. We also adapt the spin exchange model to triplet fusion and triplet energy transfer, which often occur after singlet fission in organic solids.

WIMP dark matter and unitarity-conserving inflation via a gauge singlet scalar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kahlhoefer, Felix; McDonald, John, E-mail: felix.kahlhoefer@desy.de, E-mail: j.mcdonald@lancaster.ac.uk

2015-11-01

A gauge singlet scalar with non-minimal coupling to gravity can drive inflation and later freeze out to become cold dark matter. We explore this idea by revisiting inflation in the singlet direction (S-inflation) and Higgs Portal Dark Matter in light of the Higgs discovery, limits from LUX and observations by Planck. We show that large regions of parameter space remain viable, so that successful inflation is possible and the dark matter relic abundance can be reproduced. Moreover, the scalar singlet can stabilise the electroweak vacuum and at the same time overcome the problem of unitarity-violation during inflation encountered by Higgsmore » Inflation, provided the singlet is a real scalar. The 2-σ Planck upper bound on n{sub s} imposes that the singlet mass is below 2 TeV, so that almost the entire allowed parameter range can be probed by XENON1T.« less

Singlet-triplet fission of carotenoid excitation in light-harvesting LH2 complexes of purple phototrophic bacteria.

PubMed

Klenina, I B; Makhneva, Z K; Moskalenko, A A; Gudkov, N D; Bolshakov, M A; Pavlova, E A; Proskuryakov, I I

2014-03-01

The current generally accepted structure of light-harvesting LH2 complexes from purple phototrophic bacteria conflicts with the observation of singlet-triplet carotenoid excitation fission in these complexes. In LH2 complexes from the purple bacterium Allochromatium minutissimum, a drop in the efficiency of carotenoid triplet generation is demonstrated, which correlates with the extent of selective photooxidation of bacteriochlorophylls absorbing at ~850 nm. We conclude that singlet-triplet fission of carotenoid excitation proceeds with participation of these excitonically coupled bacteriochlorophylls. In the framework of the proposed mechanism, the contradiction between LH2 structure and photophysical properties of carotenoids is eliminated. The possibility of singlet-triplet excitation fission involving a third mediator molecule was not considered earlier.

Final Progress Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Josef Michl

2011-10-31

In this project we have established guidelines for the design on organic chromophores suitable for producing high triplet yields via singlet fission. We have proven their utility by identifying a chromophore of a structural class that had never been examined for singlet fission before, 1,3-diphenylisobenzofuran, and demonstrating in two independent ways that a thin layer of this material produces a triplet yield of 200% within experimental error. We have also designed a second chromophore of a very different type, again of a structural class that had not been examined for singlet fission before, and found that in a thin layermore » it produces a 70% triplet yield. Finally, we have enhanced the theoretical understanding of the quantum mechanical nature of the singlet fission process.« less

Fully gapped spin-singlet superconductivity in noncentrosymmetric PbTaSe2: 207Pb nuclear magnetic resonance study

NASA Astrophysics Data System (ADS)

Maeda, S.; Matano, K.; Zheng, Guo-qing

2018-05-01

We report the 207Pb nuclear magnetic resonance (NMR) measurements on polycrystalline sample of PbTaSe2 with noncentrosymmetric crystal structure and topological electronic band. The nuclear spin-lattice relaxation rate 1 /T1 shows a suppressed coherence peak below the superconducting transition temperature Tc=4.05 K and decreases as an exponential function of temperature. The penetration depth derived from the NMR spectrum is almost temperature independent below T =0.7 Tc. The Knight shift K decreases below Tc. These results suggest spin-singlet superconductivity with a fully opened gap 2 Δ =3.5 kBTc in PbTaSe2.

Electronic structure of the alkyne-bridged dicobalt hexacarbonyl complex Co(2) micro-C(2)H(2) (CO)(6): evidence for singlet diradical character and implications for metal-metal bonding.

PubMed

Platts, James A; Evans, Gareth J S; Coogan, Michael P; Overgaard, Jacob

2007-08-06

A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 micro-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree-Fock (RHF) or Kohn-Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 micro-C2H2 (CO)6. CAS methods identify significant population of a Co-Co antibonding orbital, along with Co-pi* back-bonding, and a relatively large singlet-triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.

First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular π Stacking

NASA Astrophysics Data System (ADS)

Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene; Olivier, Yoann; Beljonne, David

2015-09-01

Singlet excitons in π -stacked molecular crystals can split into two triplet excitons in a process called singlet fission that opens a route to carrier multiplication in photovoltaics. To resolve controversies about the mechanism of singlet fission, we have developed a first principles nonadiabatic quantum dynamical model that reveals the critical role of molecular stacking symmetry and provides a unified picture of coherent versus thermally activated singlet fission mechanisms in different acenes. The slip-stacked equilibrium packing structure of pentacene derivatives is found to enhance ultrafast singlet fission mediated by a coherent superexchange mechanism via higher-lying charge transfer states. By contrast, the electronic couplings for singlet fission strictly vanish at the C2 h symmetric equilibrium π stacking of rubrene. In this case, singlet fission is driven by excitations of symmetry-breaking intermolecular vibrations, rationalizing the experimentally observed temperature dependence. Design rules for optimal singlet fission materials therefore need to account for the interplay of molecular π -stacking symmetry and phonon-induced coherent or thermally activated mechanisms.

"Triplet" polycistronic vectors encoding Gata4, Mef2c, and Tbx5 enhances postinfarct ventricular functional improvement compared with singlet vectors.

PubMed

Mathison, Megumi; Singh, Vivek P; Gersch, Robert P; Ramirez, Maricela O; Cooney, Austin; Kaminsky, Stephen M; Chiuchiolo, Maria J; Nasser, Ahmed; Yang, Jianchang; Crystal, Ronald G; Rosengart, Todd K

2014-10-01

The in situ reprogramming of cardiac fibroblasts into induced cardiomyocytes by the administration of gene transfer vectors encoding Gata4 (G), Mef2c (M), and Tbx5 (T) has been shown to improve ventricular function in myocardial infarction models. The efficacy of this strategy could, however, be limited by the need for fibroblast targets to be infected 3 times--once by each of the 3 transgene vectors. We hypothesized that a polycistronic "triplet" vector encoding all 3 transgenes would enhance postinfarct ventricular function compared with use of "singlet" vectors. After validation of the polycistronic vector expression in vitro, adult male Fischer 344 rats (n=6) underwent coronary ligation with or without intramyocardial administration of an adenovirus encoding all 3 major vascular endothelial growth factor (VEGF) isoforms (AdVEGF-All6A positive), followed 3 weeks later by the administration to AdVEGF-All6A-positive treated rats of singlet lentivirus encoding G, M, or T (1×10(5) transducing units each) or the same total dose of a GMT "triplet" lentivirus vector. Western blots demonstrated that triplet and singlet vectors yielded equivalent GMT transgene expression, and fluorescence activated cell sorting demonstrated that triplet vectors were nearly twice as potent as singlet vectors in generating induced cardiomyocytes from cardiac fibroblasts. Echocardiography demonstrated that GMT triplet vectors were more effective than the 3 combined singlet vectors in enhancing ventricular function from postinfarct baselines (triplet, 37%±10%; singlet, 13%±7%; negative control, 9%±5%; P<.05). These data have confirmed that the in situ administration of G, M, and T induces postinfarct ventricular functional improvement and that GMT polycistronic vectors enhance the efficacy of this strategy. Copyright © 2014 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.

Properties of the Only Thorium Fullerene, Th@C84, Uncovered.

PubMed

Kaminský, Jakub; Vícha, Jan; Bouř, Petr; Straka, Michal

2017-04-27

Only a single thorium fullerene, Th@C 84 , has been reported to date (Akiyama, K.; et al. J. Nucl. Radiochem. Sci. 2002, 3, 151-154). Although the system was characterized by UV-vis and XANES (X-ray absorption near edge structure) spectra, its structure and properties remain unknown. In this work we used the density functional calculations to identify molecular and electronic structure of the Th@C 84 . Series of molecular structures satisfying the ThC 84 stoichiometric formula were studied comprising 24 IPR and 110 non-IPR Th@C 84 isomers as well as 9 ThC 2 @C 82 IPR isomers. The lowest energy structure is Th@C 84 -C s (10) with the singlet ground state. Its predicted electronic absorption spectra are in agreement with the experimentally observed ones. The bonding between the cage and Th was characterized as polar covalent with Th in formal oxidation state IV. The NMR chemical shifts of Th@C 84 -C s (10) were predicted to guide the future experimental efforts in identification of this compound.

Excited State Studies of Polyacenes Using the All-Order Constricted Variational Density Functional Theory with Orbital Relaxation.

PubMed

Senn, Florian; Krykunov, Mykhaylo

2015-10-22

For the polyacenes series from naphthalene to hexacene, we present the vertical singlet excitation energies 1 (1)La and 1 (1)Lb, as well as the first triplet excitation energies obtained by the all-order constricted variational density functional theory with orbital relaxation (R-CV(∞)-DFT). R-CV(∞)-DFT is a further development of variational density functional theory (CV(∞)-DFT), which has already been successfully applied for the calculation of the vertical singlet excitation energies (1)La and (1)Lb for polyacenes,15 and we show that one obtains consistent excitation energies using the local density approximation as a functional for singlet as well as for triplet excitations when going beyond the linear response theory. Furthermore, we apply self-consistent field density functional theory (ΔSCF-DFT) and compare the obtained excitation energies for the first triplet excitations T1, where, due to the character of the transition, ΔSCF-DFT and R-CV(∞)-DFT become numerically equivalent, and for the singlet excitations 1 (1)La and 1 (1)Lb, where the two methods differ.

Carotenoids and Photosynthesis.

PubMed

Hashimoto, Hideki; Uragami, Chiasa; Cogdell, Richard J

2016-01-01

Carotenoids are ubiquitous and essential pigments in photosynthesis. They absorb in the blue-green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and so expand the wavelength range of light that is able to drive photosynthesis. This is an example of singlet-singlet energy transfer, and so carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. Carotenoids also act to protect photosynthetic organisms from the harmful effects of excess exposure to light. Triplet-triplet energy transfer from chlorophylls to carotenoids plays a key role in this photoprotective reaction. In the light-harvesting pigment-protein complexes from purple photosynthetic bacteria and chlorophytes, carotenoids have an additional role of structural stabilization of those complexes. In this article we review what is currently known about how carotenoids discharge these functions. The molecular architecture of photosynthetic systems will be outlined first to provide a basis from which to describe carotenoid photochemistry, which underlies most of their important functions in photosynthesis.

Electrically controllable spin filtering based on superconducting helical states

NASA Astrophysics Data System (ADS)

Bobkova, I. V.; Bobkov, A. M.

2017-12-01

The magnetoelectric effects in the surface states of the three-dimensional (3D) topological insulator (TI) are extremely strong due to the full spin-momentum locking. Here the microscopic theory of S/3D TI bilayer structures in terms of quasiclassical Green's functions is developed. On the basis of the developed formalism it is shown that the DOS in the S/TI bilayer manifests giant magnetoelectric behavior and, as a result, S/3D TI heterostructures can work as nonmagnetic fully electrically controllable spin filters. It is shown that due to the full spin-momentum locking the amplitudes of the odd-frequency singlet and triplet components of the condensate wave function are equal. The same is valid for the even frequency singlet and triplet components. We unveil the connection between the odd-frequency pairing in S/3D TI heterostructures and magnetoelectric effects in the DOS.

Magnetic resonance imaging of (1)H long lived states derived from parahydrogen induced polarization in a clinical system.

PubMed

Graafen, Dirk; Franzoni, María Belén; Schreiber, Laura M; Spiess, Hans W; Münnemann, Kerstin

2016-01-01

Hyperpolarization is a powerful tool to overcome the low sensitivity of nuclear magnetic resonance (NMR). However, applications are limited due to the short lifetime of this non equilibrium spin state caused by relaxation processes. This issue can be addressed by storing hyperpolarization in slowly decaying singlet spin states which was so far mostly demonstrated for non-proton spin pairs, e.g. (13)C-(13)C. Protons hyperpolarized by parahydrogen induced polarization (PHIP) in symmetrical molecules, are very well suited for this strategy because they naturally exhibit a long-lived singlet state. The conversion of the NMR silent singlet spin state to observable magnetization can be achieved by making use of singlet-triplet level anticrossings. In this study, a low-power radiofrequency pulse sequence is used for this purpose, which allows multiple successive singlet-triplet conversions. The generated magnetization is used to record proton images in a clinical magnetic resonance imaging (MRI) system, after 3min waiting time. Our results may open unprecedented opportunities to use the standard MRI nucleus (1)H for e.g. metabolic imaging in the future. Copyright © 2016. Published by Elsevier Inc.

Combined phosphorescence-holographic approach for singlet oxygen detection in biological media

NASA Astrophysics Data System (ADS)

Semenova, I. V.; Belashov, A. V.; Beltukova, D. M.; Petrov, N. V.; Vasyutinskii, O. S.

2015-06-01

The paper presents a novel combined approach aimed to detect and monitor singlet oxygen molecules in biological specimens by means of the simultaneous recording and monitoring of their deactivation dynamics in the two complementary channels: radiative and nonradiative. The approach involves both the direct registration of phosphorescence at the wavelength of about 1270 nm caused by radiative relaxation of excited singlet oxygen molecules and holographic recording of thermal disturbances in the medium produced by their nonradiative relaxation. The data provides a complete set of information on singlet oxygen location and dynamics in the medium. The approach was validated in the case study of photosensitized generation of singlet oxygen in onion cell structures.

A density functional theory study on the structural and electronic properties of PbxSbySez (x + y + z = 2, 3) clusters

NASA Astrophysics Data System (ADS)

Peköz, Rengi˙n; Erkoç, Şaki˙r

2018-01-01

The structural and electronic properties of neutral ternary PbxSbySez clusters (x + y + z = 2, 3) in their ground states have been explored by means of density functional theory calculations. The geometric structures and binding energies are systematically explored and for the most stable configurations of each cluster type vibrational frequencies, charges on atoms, energy difference between highest occupied and lowest unoccupied molecular orbitals, and the possible dissociations channels have been analyzed. Depending on being binary or ternary cluster and composition, the most energetic structures have singlet, doublet or triplet ground states, and trimers prefer to form isosceles, equilateral or scalene triangle structure.

Structure and capacitance of an electric double layer of an asymmetric valency dimer electrolyte: A comparison of the density functional theory with Monte Carlo simulations

DOE PAGES

Henderson, Douglas; Silvestre-Alcantara, Whasington; Kaja, Monika; ...

2016-08-18

Here, the density functional theory is applied to a study of the structure and differential capacitance of a planar electric double layer formed by a valency asymmetric mixture of charged dimers and monomers. The dimer consists of two tangentially tethered hard spheres of equal diameters of which one is charged and the other is neutral, while the monomer is a charged hard sphere of the same size. The dimer electrolyte is next to a uniformly charged, smooth planar electrode. The electrode-particle singlet distributions, the mean electrostatic potential, and the differential capacitance for the model double layer are evaluated for amore » 2:1/1:2 valency electrolyte at a given concentration. Important consequences of asymmetry in charges and in ion shapes are (i) a finite, non-zero potential of zero charge, and (ii) asymmetric shaped 2:1 and 1:2 capacitance curves which are not mirror images of each other. Comparisons of the density functional results with the corresponding Monte Carlo simulations show the theoretical predictions to be in good agreement with the simulations overall except near zero surface charge.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted B50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state thatmore » precedes formation of the pentacene triplet excitons. In conclusion, using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.« less

Unveiling a spinor field classification with non-Abelian gauge symmetries

NASA Astrophysics Data System (ADS)

Fabbri, Luca; da Rocha, Roldão

2018-05-01

A spinor fields classification with non-Abelian gauge symmetries is introduced, generalizing the U(1) gauge symmetries-based Lounesto's classification. Here, a more general classification, contrary to the Lounesto's one, encompasses spinor multiplets, corresponding to non-Abelian gauge fields. The particular case of SU(2) gauge symmetry, encompassing electroweak and electromagnetic conserved charges, is then implemented by a non-Abelian spinor classification, now involving 14 mixed classes of spinor doublets. A richer flagpole, dipole, and flag-dipole structure naturally descends from this general classification. The Lounesto's classification of spinors is shown to arise as a Pauli's singlet, into this more general classification.

Does the concept of Clar's aromatic sextet work for dicationic forms of polycyclic aromatic hydrocarbons?--testing the model against charged systems in singlet and triplet states.

PubMed

Dominikowska, Justyna; Palusiak, Marcin

2011-07-07

The concept of Clar's π-electron aromatic sextet was tested against a set of polycyclic aromatic hydrocarbons in neutral and doubly charged forms. Systems containing different types of rings (in the context of Clar's concept) were chosen, including benzene, naphthalene, anthracene, phenanthrene and triphenylene. In the case of dicationic structures both singlet and triplet states were considered. It was found that for singlet state dicationic structures the concept of aromatic sextet could be applied and the local aromaticity could be discussed in the context of that model, whereas in the case of triplet state dicationic structures Clar's model rather failed. Different aromaticity indices based on various properties of molecular systems were applied for the purpose of the studies. The discussion about the interdependence between the values of different aromaticity indices applied to neutral and charged systems in singlet and triplet states is also included. This journal is © the Owner Societies 2011

Structural physical approximation for the realization of the optimal singlet fraction with two measurements

NASA Astrophysics Data System (ADS)

Adhikari, Satyabrata

2018-04-01

Structural physical approximation (SPA) has been exploited to approximate nonphysical operation such as partial transpose. It has already been studied in the context of detection of entanglement and found that if the minimum eigenvalue of SPA to partial transpose is less than 2/9 then the two-qubit state is entangled. We find application of SPA to partial transpose in the estimation of the optimal singlet fraction. We show that the optimal singlet fraction can be expressed in terms of the minimum eigenvalue of SPA to partial transpose. We also show that the optimal singlet fraction can be realized using Hong-Ou-Mandel interferometry with only two detectors. Further we have shown that the generated hybrid entangled state between a qubit and a binary coherent state can be used as a resource state in quantum teleportation.

Towards building artificial light harvesting complexes: enhanced singlet-singlet energy transfer between donor and acceptor pairs bound to albumins.

PubMed

Kumar, Challa V; Duff, Michael R

2008-12-01

Specific donor and acceptor pairs have been assembled in bovine serum albumin (BSA), at neutral pH and room temperature, and these dye-protein complexes indicated efficient donor to acceptor singlet-singlet energy transfer. For example, pyrene-1-butyric acid served as the donor and Coumarin 540A served as the acceptor. Both the donor and the acceptor bind to BSA with affinity constants in excess of 2x10(5) M(-1), as measured in absorption and circular dichroism (CD) spectral titrations. Simultaneous binding of both the donor and the acceptor chromophores was supported by CD spectra and one chromophore did not displace the other from the protein host, even when limited concentrations of the host were used. For example, a 1:1:1 complex between the donor, acceptor and the host can be readily formed, and spectral data clearly show that the binding sites are mutually exclusive. The ternary complexes (two different ligands bound to the same protein molecule) provided opportunities to examine singlet-singlet energy transfer between the protein-bound chromophores. Donor emission was quenched by the addition of the acceptor, in the presence of limited amounts of BSA, while no energy transfer was observed in the absence of the protein host, under the same conditions. The excitation spectra of the donor-acceptor-host complexes clearly show the sensitization of acceptor emission by the donor. Protein denaturation, as induced by the addition of urea or increasing the temperature to 360 K, inhibited energy transfer, which indicate that protein structure plays an important role. Sensitization also proceeded at low temperature (77 K) and diffusion of the donor or the acceptor is not required for energy transfer. Stern-Volmer quenching plots show that the quenching constant is (3.1+/-0.2)x10(4) M(-1), at low acceptor concentrations (<35 microM). Other albumins such as human and porcine proteins also served as good hosts for the above experiments. For the first time, non-natural systems have been self-assembled which can capture donor-acceptor pairs and facilitate singlet-singlet energy transfer. Such systems may form a basis for the design and construction of protein-based multi-chromophore self-assemblies for solar light harvesting, conversion and storage.

Different mechanisms for the photoinduced production of oxidative DNA damage by fluoroquinolones differing in photostability.

PubMed

Spratt, T E; Schultz, S S; Levy, D E; Chen, D; Schlüter, G; Williams, G M

1999-09-01

Several fluoroquinolone antibacterial agents exhibit an adverse phototoxic effect in humans and are photo-cocarcinogenic in mice. The UV-induced production of reactive oxygen species plays a role in the toxicity and may be involved in carcinogenicity. Four fluoroquinolones were examined for the ability to photochemically produce oxidative damage in naked DNA. The major structural difference in the fluoroquinolones that would have an effect on their photostability is the functionality at the 8-position. At this position, 1-cyclopropyl-7-(2,8-diazbicyclo[4.3.0]non-8-yl)-6, 8-difluoro-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid (BAY y3118) contains a chlorine atom, lomefloxacin a fluorine atom, ciprofloxacin a proton, and moxifloxacin a methoxy group. The formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) in calf thymus DNA was assessed by HPLC with electrochemical detection, and strand breaks were measured in pBR322 with agarose gel electrophoresis. The relative photolability of the fluoroquinolones correlated to the extent of production of 8-oxodGuo and strand breaks, with both UVA and UVB irradiation, in the following order: BAY y3118 approximately lomefloxacin > ciprofloxacin > moxifloxacin. Experiments were performed to determine whether the mechanism of damage was due to a type I (radical) or type II (singlet oxygen) pathway. Nitrogen depletion of oxygen resulted in a decrease in the extent of formation of 8-oxodGuo, suggesting that oxygen was involved. The use of selective radical or singlet oxygen inhibitors was inconclusive with respect to which pathway was involved. The use of D(2)O as a solvent, which would extend the lifetime of singlet oxygen, suggested that this species is involved in the formation of 8-oxodGuo by moxifloxacin and ciprofloxacin, but not by lomefloxacin and BAY y3118. Similarly, it was found that singlet oxygen was not involved in strand break formation. Thus, the evidence suggests that fluoroquinolones can photochemically produce DNA damage by both type I and type II mechanisms.

Tensor network methods for the simulation of open quantum dynamics in multichromophore systems: Application to singlet fission in novel pentacene dimers

NASA Astrophysics Data System (ADS)

Chin, Alex

Singlet fission (SF) is an ultrafast process in which a singlet exciton spontaneously converts into a pair of entangled triplet excitons on neighbouring organic molecules. As a mechanism of multiple exciton generation, it has been suggested as a way to increase the efficiency of organic photovoltaic devices, and its underlying photophysics across a wide range of molecules and materials has attracted significant theoretical attention. Recently, a number of studies using ultrafast nonlinear optics have underscored the importance of intramolecular vibrational dynamics in efficient SF systems, prompting a need for methods capable of simulating open quantum dynamics in the presence of highly structured and strongly coupled environments. Here, a combination of ab initio electronic structure techniques and a new tensor-network methodology for simulating open vibronic dynamics is presented and applied to a recently synthesised dimer of pentacene (DP-Mes). We show that ultrafast (300 fs) SF in this system is driven entirely by symmetry breaking vibrations, and our many-body approach enables the real-time identification and tracking of the ''functional' vibrational dynamics and the role of the ''bath''-like parts of the environment. Deeper analysis of the emerging wave functions points to interesting links between the time at which parts of the environment become relevant to the SF process and the optimal topology of the tensor networks, highlighting the additional insight provided by moving the problem into the natural language of correlated quantum states and how this could lead to simulations of much larger multichromophore systems Supported by The Winton Programme for the Physics of Sustainability.

Photosensitized generation of singlet oxygen in porous silicon studied by simultaneous measurements of luminescence of nanocrystals and oxygen molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gongalsky, M. B.; Kharin, A. Yu.; Zagorodskikh, S. A.

2011-07-01

Photosensitization of singlet oxygen generation in porous silicon (PSi) was investigated by simultaneous measurements of the photoluminescence (PL) of silicon nanocrystals (nc-Si) and the infrared emission of the {sup 1}{Delta}-state of oxygen molecules at 1270 nm (0.98 eV) at room temperature. Photodegradation of the nc-Si PL properties was found to correlate with the efficiency of singlet oxygen generation. The quantum efficiency of singlet oxygen generation in PSi was estimated to be about 1%, while the lifetime of singlet oxygen was about fifteen ms. The kinetics of nc-Si PL intensity under cw excitation undergoes a power law dependence with the exponentmore » dependent on the photon energy of luminescence. The experimental results are explained with a model of photodegradation controlled by the diffusion of singlet oxygen molecules in a disordered structure of porous silicon.« less

Solid-phase fullerene-like nanostructures as singlet oxygen photosensitizers in liquid media

NASA Astrophysics Data System (ADS)

Belousova, I. M.; Danilov, O. B.; Kiselev, V. M.; Kislyakov, I. M.; Kris'ko, T. K.; Murav'eva, T. D.; Videnichev, D. A.

2007-04-01

Singlet oxygen generation by fullerene and astralen containing surfaces and powders under visible irradiation was studied in water and organic liquids by means of 1Δ g state luminescence and chemical scavenger transmittance measurements. The chemical method, pioneered for solid photosensitizers of 10 II, allowed to measure the singlet oxygen concentration in the aqueous medium down to 10 8 cm -3. The singlet oxygen sensitizing by the solid-phase fullerene-containing systems was found to be 100 times less effective then by fullerene in solution. The results obtained confirm the applicability of these structures in biology and medicine.

Collisional spin-oriented Sherman function in electron-hole semiconductor plasmas: Landau damping effect

NASA Astrophysics Data System (ADS)

Lee, Myoung-Jae; Jung, Young-Dae

2018-04-01

The influence of Landau damping on the spin-oriented collisional asymmetry is investigated in electron-hole semiconductor plasmas. The analytical expressions of the spin-singlet and the spin-triplet scattering amplitudes as well as the spin-oriented asymmetry Sherman function are obtained as functions of the scattering angle, the Landau parameter, the effective Debye length, and the collision energy. It is found that the Landau damping effect enhances the spin-singlet and spin-triplet scattering amplitudes in the forward and back scattering domains, respectively. It is also found that the Sherman function increases with an increase in the Landau parameter. In addition, the spin-singlet scattering process is found to be dominant rather than the spin-triplet scattering process in the high collision energy domain.

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission† †Electronic supplementary information (ESI) available: Actinic pump spectrum, discussion on ground state addition process, peak fitting procedure, transient absorption data, power dependence measurements, etalon pulse shaping, TIPS-pentacene FSRS data, and optimized geometry and frequency calculation results. See DOI: 10.1039/c7sc03496b

PubMed Central

Hart, Stephanie M.; Silva, W. Ruchira

2017-01-01

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes. PMID:29675170

A new analytical potential energy surface for the singlet state of He{sub 2}H{sup +}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang Jingjuan; Zhang Qinggang; Yang Chuanlu

2012-03-07

The analytic potential energy surface (APES) for the exchange reaction of HeH{sup +} (X{sup 1}{Sigma}{sup +}) + He at the lowest singlet state 1{sup 1}A{sup /} has been built. The APES is expressed as Aguado-Paniagua function based on the many-body expansion. Using the adaptive non-linear least-squares algorithm, the APES is fitted from 15 682 ab initio energy points calculated with the multireference configuration interaction calculation with a large d-aug-cc-pV5Z basis set. To testify the new APES, we calculate the integral cross sections for He + H{sup +}He (v= 0, 1, 2, j= 0) {yields} HeH{sup +}+ He by means ofmore » quasi-classical trajectory and compare them with the previous result in literature.« less

Superconductivity and spin-orbit coupling in non-centrosymmetric materials: a review

NASA Astrophysics Data System (ADS)

Smidman, M.; Salamon, M. B.; Yuan, H. Q.; Agterberg, D. F.

2017-03-01

In non-centrosymmetric superconductors, where the crystal structure lacks a centre of inversion, parity is no longer a good quantum number and an electronic antisymmetric spin-orbit coupling (ASOC) is allowed to exist by symmetry. If this ASOC is sufficiently large, it has profound consequences on the superconducting state. For example, it generally leads to a superconducting pairing state which is a mixture of spin-singlet and spin-triplet components. The possibility of such novel pairing states, as well as the potential for observing a variety of unusual behaviors, led to intensive theoretical and experimental investigations. Here we review the experimental and theoretical results for superconducting systems lacking inversion symmetry. Firstly we give a conceptual overview of the key theoretical results. We then review the experimental properties of both strongly and weakly correlated bulk materials, as well as two dimensional systems. Here the focus is on evaluating the effects of ASOC on the superconducting properties and the extent to which there is evidence for singlet-triplet mixing. This is followed by a more detailed overview of theoretical aspects of non-centrosymmetric superconductivity. This includes the effects of the ASOC on the pairing symmetry and the superconducting magnetic response, magneto-electric effects, superconducting finite momentum pairing states, and the potential for non-centrosymmetric superconductors to display topological superconductivity.

Multistate photo-induced relaxation and photoisomerization ability of fumaramide threads: a computational and experimental study.

PubMed

Altoè, Piero; Haraszkiewicz, Natalia; Gatti, Francesco G; Wiering, Piet G; Frochot, Céline; Brouwer, Albert M; Balkowski, Grzegorz; Shaw, Daniel; Woutersen, Sander; Buma, Wybren Jan; Zerbetto, Francesco; Orlandi, Giorgio; Leigh, David A; Garavelli, Marco

2009-01-14

Fumaric and maleic amides are the photoactive units of an important and widely investigated class of photocontrollable rotaxanes as they trigger ring shuttling via a cis-trans photoisomerization. Here, ultrafast decay and photoinduced isomerization in isolated fumaramide and solvated nitrogen-substituted fumaramides (that are employed as threads in those rotaxanes) have been investigated by means of CASPT2//CASSCF computational and time-resolved spectroscopic techniques, respectively. A complex multistate network of competitive deactivation channels, involving both internal conversion and intersystem crossing (ISC) processes, has been detected and characterized that accounts for the picosecond decay and photochemical/photophysical properties observed in the singlet as well as triplet (photosensitized) photochemistry of fumaramides threads. Interestingly, singlet photochemistry appears to follow a non-Kasha rule model, where nonequilibrium dynamical factors control the outcome of the photochemical process: accessible high energy portions of extended crossing seams turn out to drive the deactivation process and ground-state recovery. Concurrently, extended singlet/triplet degenerate regions of twisted molecular structures with significant spin-orbit-coupling values account for ultrafast (picosecond time scale) ISC processes that lead to higher photoisomerization efficiencies. This model discloses the principles behind the intrinsic photochemical reactivity of fumaramide and its control.

Adapting BODIPYs to singlet oxygen production on silica nanoparticles.

PubMed

Epelde-Elezcano, Nerea; Prieto-Montero, Ruth; Martínez-Martínez, Virginia; Ortiz, María J; Prieto-Castañeda, Alejandro; Peña-Cabrera, Eduardo; Belmonte-Vázquez, José L; López-Arbeloa, Iñigo; Brown, Ross; Lacombe, Sylvie

2017-05-31

A modified Stöber method is used to synthesize spherical core-shell silica nanoparticles (NPs) with an external surface functionalized by amino groups and with an average size around 50 nm. Fluorescent dyes and photosensitizers of singlet oxygen were fixed, either separately or conjointly, respectively in the core or in the shell. Rhodamines were encapsulated in the core with relatively high fluorescence quantum yields (Φ fl ≥ 0.3), allowing fluorescence tracking of the particles. Various photosensitizers of singlet oxygen (PS) were covalenty coupled to the shell, allowing singlet oxygen production. The stability of NP suspensions strongly deteriorated upon grafting the PS, affecting their apparent singlet oxygen quantum yields. Agglomeration of NPs depends both on the type and on the amount of grafted photosensitizer. New, lab-made, halogenated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPY) grafted to the NPs achieved higher singlet oxygen quantum yields (Φ Δ ∼ 0.35-0.40) than Rose Bengal (RB) grafted NPs (Φ Δ ∼ 0.10-0.27). Finally, we combined both fluorescence and PS functions in the same NP, namely a rhodamine in the silica core and a BODIPY or RB grafted in the shell, achieving the performance Φ fl ∼ 0.10-0.20, Φ Δ ∼ 0.16-0.25 with a single excitation wavelength. Thus, proper choice of the dyes, of their concentrations inside and on the NPs and the grafting method enables fine-tuning of singlet oxygen production and fluorescence emission.

Rapid assessment of singlet oxygen-induced plasma lipid oxidation and its inhibition by antioxidants with diphenyl-1-pyrenylphosphine (DPPP).

PubMed

Morita, Mayuko; Naito, Yuji; Yoshikawa, Toshikazu; Niki, Etsuo

2016-01-01

Recent studies suggesting the involvement of singlet oxygen in the pathogenesis of multiple diseases have attracted renewed attention to lipid oxidation mediated by singlet oxygen. Although the rate constants for singlet oxygen quenching by antioxidants have been measured extensively, the inhibition of lipid oxidation mediated by singlet oxygen has received relatively less attention, partly because a convenient method for measuring the rate of lipid oxidation is not available. The objective of this study was to develop a convenient method to measure plasma lipid oxidation mediated by singlet oxygen which may be applied to a rapid assessment of the antioxidant capacity to inhibit this oxidation using a conventional microplate reader. Singlet oxygen was produced from naphthalene endoperoxide, and lipid hydroperoxide production was followed by using diphenyl-1-pyrenylphosphine (DPPP). Non-fluorescent DPPP reacts stoichiometrically with lipid hydroperoxides to give highly fluorescent DPPP oxide. It was found that plasma oxidation by singlet oxygen increased the fluorescence intensity of DPPP oxide, which was suppressed by antioxidants. Fucoxanthin suppressed the oxidation more efficiently than β-carotene and α-tocopherol, while ascorbic acid and Trolox were not effective. The present method may be useful for monitoring lipid oxidation and also for rapid screening of the capacity of dietary antioxidants and natural products to inhibit lipid oxidation in a biologically relevant system.

Scattering amplitude and bosonization duality in general Chern-Simons vector models

NASA Astrophysics Data System (ADS)

Yokoyama, Shuichi

2016-09-01

We present the exact large N calculus of four point functions in general Chern-Simons bosonic and fermionic vector models. Applying the LSZ formula to the four point function we determine the two body scattering amplitudes in these theories taking a special care for a non-analytic term to achieve unitarity in the singlet channel. We show that the S-matrix enjoys the bosonization duality, an unusual crossing relation and a non-relativistic reduction to Aharonov-Bohm scattering. We also argue that the S-matrix develops a pole in a certain range of coupling constants, which disappears in the range where the theory reduces to the Chern-Simons theory interacting with free fermions.

An improved analysis of proton structure function F2(x,t) at small x

NASA Astrophysics Data System (ADS)

Machahari, Luxmi; Choudhury, D. K.

2018-04-01

We report an improved analysis of Taylor approximated coupled DGLAP equations for singlet F2S(x,t) and gluon G( x, t) distributions at small x pursued in recent years. To that end, we assume a plausible t-dependent relation between the singlet and gluon distribution valid at small x and omit the boundary condition F2S (1, t) = 0, for any t which needs large x extrapolation of small x solution. We observe that in general two inequivalent t-evolutions of F2S (x, t) and G( x, t) are possible. Theoretical advantages of one over the other are discussed and compared with the recently compiled data in order to choose the best one. Phenomenological range of validity of solutions is also reported.

Proof of factorization of χ _{cJ} production in non-equilibrium QCD at RHIC and LHC in color singlet mechanism

NASA Astrophysics Data System (ADS)

Nayak, Gouranga C.

2017-12-01

Recently we have proved the factorization of NRQCD S-wave heavy quarkonium production at all orders in coupling constant. In this paper we extend this to prove the factorization of infrared divergences in χ _{cJ} production from color singlet c{\\bar{c}} pair in non-equilibrium QCD at RHIC and LHC at all orders in coupling constant. This can be relevant to study the quark-gluon plasma at RHIC and LHC.

Sentan: A Novel Specific Component of the Apical Structure of Vertebrate Motile Cilia

PubMed Central

Yuba-Kubo, Akiko; Tsukita, Sachiko; Tsukita, Shoichiro; Amagai, Masayuki

2008-01-01

Human respiratory and oviductal cilia have specific apical structures characterized by a narrowed distal portion and a ciliary crown. These structures are conserved among vertebrates that have air respiration systems; however, the molecular components of these structures have not been defined, and their functions are unknown. To identify the molecular component(s) of the cilia apical structure, we screened EST libraries to identify gene(s) that are exclusively expressed in ciliated tissues, are transcriptionally up-regulated during in vitro ciliogenesis, and are not expressed in testis (because sperm flagella have no such apical structures). One of the identified gene products, named sentan, was localized to the distal tip region of motile cilia. Using anti-sentan polyclonal antibodies and electron microscopy, sentan was shown to localize exclusively to the bridging structure between the cell membrane and peripheral singlet microtubules, which specifically exists in the narrowed distal portion of cilia. Exogenously expressed sentan showed affinity for the membrane protrusions, and a protein–lipid binding assay revealed that sentan bound to phosphatidylserine. These findings suggest that sentan is the first molecular component of the ciliary tip to bridge the cell membrane and peripheral singlet microtubules, making the distal portion of the cilia narrow and stiff to allow for better airway clearance or ovum transport. PMID:18829862

Effects of molecular packing in organic crystals on singlet fission with ab initio many body perturbation theory

NASA Astrophysics Data System (ADS)

Haber, Jonah; Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

Multi-exciton generation processes, in which multiple charge carriers are generated from a single photon, are mechanisms of significant interest for achieving efficiencies beyond the Shockley-Queisser limit of conventional p-n junction solar cells. One well-studied multiexciton process is singlet fission, whereby a singlet decays into two spin-correlated triplet excitons. Here, we use a newly developed computational approach to calculate singlet-fission coupling terms and rates with an ab initio Green's function formalism based on many-body perturbation theory (MBPT) within the GW approximation and the Bethe-Salpeter equation approach. We compare results for crystalline pentacene and TIPS-pentacene and explore the effect of molecular packing on the singlet fission mechanism. This work is supported by the Department of Energy.

Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

PubMed

Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

2009-10-15

A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster.

PubMed

Schenk, Christian; Kracke, Andreas; Fink, Karin; Kubas, Adam; Klopper, Wim; Neumaier, Marco; Schnöckel, Hansgeorg; Schnepf, Andreas

2011-03-02

The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.

Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz-Sanchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel

2008-12-07

The ultrafast proton transfer dynamics of salicylideneaniline has been theoretically analyzed in the ground and first singlet excited electronic states using density functional theory (DFT) and time-dependent DFT calculations, which predict a ({pi},{pi}*) barrierless excited state intramolecular proton transfer (ESIPT). In addition to this, the photochemistry of salicylideneaniline is experimentally known to present fast depopulation processes of the photoexcited species before and after the proton transfer reaction. Such processes are explained by means of conical intersections between the ground and first singlet ({pi},{pi}*) excited electronic states. The electronic energies obtained by the time-dependent density functional theory formalism have been fittedmore » to a monodimensional potential energy surface in order to perform quantum dynamics study of the processes. Our results show that the proton transfer and deactivation of the photoexcited species before the ESIPT processes are completed within 49.6 and 37.7 fs, respectively, which is in remarkable good agreement with experiments.« less

Non-perturbative determination of improvement b-coefficients in Nf = 3

NASA Astrophysics Data System (ADS)

Giulia Maria de Divitiis1, 2**, Maurizio Firrotta1, 2, Jochen Heitger3, Carl Christian Köster3; Anastassios Vladikas2

2018-03-01

We present our preliminary results of the non-perturbative determination of the valence mass dependent coefficients bA - bP and bm as well as the ratio ZPZm=ZA entering the flavour non-singlet PCAC relation in lattice QCD with Nf = 3 dynamical flavours. We apply the method proposed in the past for quenched approximation and Nf = 2 cases, employing a set of finite-volume ALPHA configurations with Schrödinger functional boundary conditions, generated with O(a) improved Wilson fermions and the tree-level Symanzik-improved gauge action for a range of couplings relevant for simulations at lattice spacings of about 0.09 fm and below.

Phthalocyanines functionalized with 2-methyl-5-nitro-1H-imidazolylethoxy and 1,4,7-trioxanonyl moieties and the effect of metronidazole substitution on photocytotoxicity.

PubMed

Wierzchowski, Marcin; Sobotta, Lukasz; Skupin-Mrugalska, Paulina; Kruk, Justyna; Jusiak, Weronika; Yee, Michael; Konopka, Krystyna; Düzgüneş, Nejat; Tykarska, Ewa; Gdaniec, Maria; Mielcarek, Jadwiga; Goslinski, Tomasz

2013-10-01

Four novel magnesium(II) and zinc(II) phthalocyanines bearing 1,4,7-trioxanonyl, polyether and/or (2-methyl-5-nitro-1H-imidazol-1-yl)ethoxy, heterocyclic substituents at their non-peripheral positions were synthesized and assessed in terms of physicochemical and biological properties. Magnesium phthalocyanine derivatives bearing polyether substituents (Pc-1), a mixed system of polyether and heterocyclic substituents (Pc-3), and four heterocyclic substituents (Pc-4), respectively, were synthesized following the Linstead macrocyclization reaction procedure. Zinc phthalocyanine (Pc-2) bearing polyether substituents at non-peripheral positions was synthesized following the procedure in n-pentanol with the zinc acetate, and DBU. Novel phthalocyanines were purified by flash column chromatography and characterized using NMR, MS, UV-Vis and HPLC. Moreover, two precursors in macrocyclization reaction phthalonitriles were characterized using X-ray. Photophysical properties of the novel macrocycles were evaluated, including UV-Vis spectra analysis and aggregation study. All macrocycles subjected to singlet oxygen generation and the oxidation rate constant measurements exhibited lower quantum yields of singlet oxygen generation in DMSO than in DMF. In addition, the Pc-2 molecule was found to be the most efficient singlet oxygen generator from the group of macrocycles studied. The photocytotoxicity evaluated on the human oral squamous cell carcinoma cell line, HSC-3, for Pc-3 was significantly higher than that for Pc-1, Pc-2, and Pc-4. Interestingly, Pc-3 was found to be the most active macrocycle in vitro although its ability to generate singlet oxygen was significantly lower than those of Pc-1 and Pc-2. However, attempts to encapsulate phthalocyanines Pc-1-Pc-3 in liposomal membranes were unsuccessful. The phthalocyanine-nitroimidazole conjugate, Pc-4 was encapsulated in phosphatidylglycerol:phosphatidylcholine unilamellar liposomes and subjected to photocytotoxicity study. © 2013.

Singlet-Oxygen Generation From Individual Semiconducting and Metallic Nanostructures During Near-Infrared Laser Trapping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Bennett E.; Roder, Paden B.; Hanson, Jennifer L.

2015-03-13

Photodynamic therapy has been used for several decades in the treatment of solid tumors through the generation of reactive singlet-oxygen species (1O2). Recently, nanoscale metallic and semiconducting materials have been reported to act as photosensitizing agents with additional diagnostic and therapeutic functionality. To date there have been no reports of observing the generation of singlet-oxygen at the level of single nanostructures, particularly at near infrared (NIR) wavelengths. Here we demonstrate that NIR laser-tweezers can be used to observe the formation of singlet-oxygen produced from individual silicon and gold nanowires via use of a commercially available reporting dye. The laser trapmore » also induces 2-photon photoexcitation of the dye following a chemical reaction with singlet oxygen. Corresponding 2-photon emission spectra confirms the generation of singlet oxygen from individual silicon nanowires at room temperature (30°C), suggesting a range of applications in understanding the impact of 1O2 on individual cancer cells.« less

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

PubMed

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

Flavor structure of Λ baryons from lattice QCD: From strange to charm quarks

NASA Astrophysics Data System (ADS)

Gubler, Philipp; Takahashi, Toru T.; Oka, Makoto

2016-12-01

We study Λ baryons of spin-parity 1/2± with either a strange or charm valence quark in full 2 +1 flavor lattice QCD. Multiple S U (3 ) singlet and octet operators are employed to generate the desired single baryon states on the lattice. Via the variational method, the couplings of these states to the different operators provide information about the flavor structure of the Λ baryons. We make use of the gauge configurations of the PACS-CS Collaboration and chirally extrapolate the results for the masses and S U (3 ) flavor components to the physical point. We furthermore gradually change the hopping parameter of the heaviest quark from strange to charm to study how the properties of the Λ baryons evolve as a function of the heavy quark mass. It is found that the baryon energy levels increase almost linearly with the quark mass. Meanwhile, the flavor structure of most of the states remains stable, with the exception of the lowest 1/2- state, which changes from a flavor singlet Λ to a Λc state with singlet and octet components of comparable size. Finally, we discuss whether our findings can be interpreted with the help of a simple quark model and find that the negative-parity Λc states can be naturally explained as diquark excitations of the light u and d quarks. On the other hand, the quark-model picture does not appear to be adequate for the negative-parity Λ states, suggesting the importance of other degrees of freedom to describe them.

Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative.

PubMed

Folie, Brendan D; Haber, Jonah B; Refaely-Abramson, Sivan; Neaton, Jeffrey B; Ginsberg, Naomi S

2018-02-14

Singlet fission is the spin-conserving process by which a singlet exciton splits into two triplet excitons. Singlet fission occurs via a correlated triplet pair intermediate, but direct evidence of this state has been scant, and in films of TIPS-pentacene, a small molecule organic semiconductor, even the rate of fission has been unclear. We use polarization-resolved transient absorption microscopy on individual crystalline domains of TIPS-pentacene to establish the fission rate and demonstrate that the initially created triplets remain bound for a surprisingly long time, hundreds of picoseconds, before separating. Furthermore, using a broadband probe, we show that it is possible to determine absorbance spectra of individual excited species in a crystalline solid. We find that triplet interactions perturb the absorbance, and provide evidence that triplet interaction and binding could be caused by the π-stacked geometry. Elucidating the relationship between the lattice structure and the electronic structure and dynamics has important implications for the creation of photovoltaic devices that aim to boost efficiency via singlet fission.

Direct dynamics simulation of dioxetane formation and decomposition via the singlet .O-O-CH2-CH2. biradical: Non-RRKM dynamics

NASA Astrophysics Data System (ADS)

Sun, Rui; Park, Kyoyeon; de Jong, Wibe A.; Lischka, Hans; Windus, Theresa L.; Hase, William L.

2012-07-01

Electronic structure calculations and direct chemical dynamics simulations are used to study the formation and decomposition of dioxetane on its ground state singlet potential energy surface. The stationary points for 1O2 + C2H4, the singlet .O-O-CH2-CH2. biradical, the transition state (TS) connecting this biradical with dioxetane, and the two transition states and gauche .O-CH2-CH2-O. biradical connecting dioxetane with the formaldehyde product molecules are investigated at different levels of electronic structure theory including UB3LYP, UMP2, MRMP2, and CASSCF and a range of basis sets. The UB3LYP/6-31G* method was found to give representative energies for the reactive system and was used as a model for the simulations. UB3LYP/6-31G* direct dynamics trajectories were initiated at the TS connecting the .O-O-CH2-CH2. biradical and dioxetane by sampling the TS's vibrational energy levels, and rotational and reaction coordinate energies, with Boltzmann distributions at 300, 1000, and 1500 K. This corresponds to the transition state theory model for trajectories that pass the TS. The trajectories were directed randomly towards both the biradical and dioxetane. A small fraction of the trajectories directed towards the biradical recrossed the TS and formed dioxetane. The remainder formed 1O2 + C2H4 and of these ˜ 40% went directly from the TS to 1O2 + C2H4 without getting trapped and forming an intermediate in the .O-O-CH2-CH2. biradical potential energy minimum, a non-statistical result. The dioxetane molecules which are formed dissociate to two formaldehyde molecules with a rate constant two orders of magnitude smaller than that predicted by Rice-Ramsperger-Kassel-Marcus theory. The reaction dynamics from dioxetane to the formaldehyde molecules do not follow the intrinsic reaction coordinate or involve trapping in the gauche .O-CH2-CH2-O. biradical potential energy minimum. Important non-statistical dynamics are exhibited for this reactive system.

Estimation of splitting functions from Earth's normal mode spectra using the neighbourhood algorithm

NASA Astrophysics Data System (ADS)

Pachhai, Surya; Tkalčić, Hrvoje; Masters, Guy

2016-01-01

The inverse problem for Earth structure from normal mode data is strongly non-linear and can be inherently non-unique. Traditionally, the inversion is linearized by taking partial derivatives of the complex spectra with respect to the model parameters (i.e. structure coefficients), and solved in an iterative fashion. This method requires that the earthquake source model is known. However, the release of energy in large earthquakes used for the analysis of Earth's normal modes is not simple. A point source approximation is often inadequate, and a more complete account of energy release at the source is required. In addition, many earthquakes are required for the solution to be insensitive to the initial constraints and regularization. In contrast to an iterative approach, the autoregressive linear inversion technique conveniently avoids the need for earthquake source parameters, but it also requires a number of events to achieve full convergence when a single event does not excite all singlets well. To build on previous improvements, we develop a technique to estimate structure coefficients (and consequently, the splitting functions) using a derivative-free parameter search, known as neighbourhood algorithm (NA). We implement an efficient forward method derived using the autoregresssion of receiver strips, and this allows us to search over a multiplicity of structure coefficients in a relatively short time. After demonstrating feasibility of the use of NA in synthetic cases, we apply it to observations of the inner core sensitive mode 13S2. The splitting function of this mode is dominated by spherical harmonic degree 2 axisymmetric structure and is consistent with the results obtained from the autoregressive linear inversion. The sensitivity analysis of multiple events confirms the importance of the Bolivia, 1994 earthquake. When this event is used in the analysis, as little as two events are sufficient to constrain the splitting functions of 13S2 mode. Apart from not requiring the knowledge of earthquake source, the newly developed technique provides an approximate uncertainty measure of the structure coefficients and allows us to control the type of structure solved for, for example to establish if elastic structure is sufficient.

Phosphorescence Kinetics of Singlet Oxygen Produced by Photosensitization in Spherical Nanoparticles. Part II. The Case of Hypericin-Loaded Low-Density Lipoprotein Particles.

PubMed

Datta, Shubhashis; Hovan, Andrej; Jutková, Annamária; Kruglik, Sergei G; Jancura, Daniel; Miskovsky, Pavol; Bánó, Gregor

2018-05-24

The phosphorescence kinetics of singlet oxygen produced by photosensitized hypericin (Hyp) molecules inside low-density lipoprotein (LDL) particles was studied experimentally and by means of numerical and analytical modeling. The phosphorescence signal was measured after short laser pulse irradiation of aqueous Hyp/LDL solutions. The Hyp triplet state lifetime determined by a laser flash-photolysis measurement was 5.3 × 10 -6 s. The numerical and the analytical model described in part I of the present work (DOI: 10.1021/acs.jpcb.8b00658) were used to analyze the observed phosphorescence kinetics of singlet oxygen. It was shown that singlet oxygen diffuses out of LDL particles on a time scale shorter than 0.1 μs. The total (integrated) concentration of singlet oxygen inside LDL is more than an order of magnitude smaller than the total singlet oxygen concentration in the solvent. The time course of singlet oxygen concentrations inside and outside the particles was calculated using simplified representations of the LDL internal structure. The experimental phosphorescence data were fitted by a linear combination of these concentrations using the emission factor E (the ratio of the radiative singlet oxygen depopulation rate constants inside and outside LDL) as a fitting parameter. The emission factor was determined to be E = 6.7 ± 2.5. Control measurements were carried out by adding sodium azide, a strong singlet oxygen quencher, to the solution.

To gauge or not to gauge?

NASA Astrophysics Data System (ADS)

Maldacena, Juan; Milekhin, Alexey

2018-04-01

The D0 brane, or BFSS, matrix model is a quantum mechanical theory with an interesting gravity dual. We consider a variant of this model where we treat the SU( N) symmetry as a global symmetry, rather than as a gauge symmetry. This variant contains new non-singlet states. We consider the impact of these new states on its gravity dual. We argue that the gravity dual is essentially the same as the one for the original matrix model. The non-singlet states have higher energy at strong coupling and are therefore dynamically suppressed.

Superconductivity from fractionalized excitations in URu2Si2

NASA Astrophysics Data System (ADS)

Hsu, Chen-Hsuan; Chakravarty, Sudip

2014-10-01

An unconventional pairing mechanism in the heavy-fermion material URu2Si2 is studied. We propose a mixed singlet-triplet d-density wave to be the hidden-order state in URu2Si2. The exotic order is topologically nontrivial and supports a charge 2e skyrmionic spin texture, which is assumed to fractionalize into merons and antimerons at the deconfined quantum critical point. The interaction between these fractional particles results in a (pseudo)spin-singlet chiral d-wave superconducting state, which breaks time-reversal symmetry. Therefore, it is highly likely to produce a nonzero signal of the polar Kerr effect at the onset of the superconductivity, consistent with recent experiments. In addition, the nodal structures of the possible pairing functions in our model are consistent with the thermodynamic experiments in URu2Si2.

Breakdown of the Wigner-Mattis theorem in semiconductor carbon-nanotube quantum dots

NASA Astrophysics Data System (ADS)

Rontani, Massimo; Secchi, Andrea; Manghi, Franca

2009-03-01

The Wigner-Mattis theorem states the ground state of two bound electrons, in the absence of the magnetic field, is always a spin-singlet. We predict the opposite result --a triplet- for two electrons in a quantum dot defined in a semiconductor carbon nanotube. The claim is supported by extensive many-body calculations based on the accurate configuration interaction code DONRODRIGO (www.s3.infm.t/donrodrigo). The crux of the matter is the peculiar two-valley structure of low-energy states, which encodes a pseudo-spin degree of freedom. The spin polarization of the ground state corresponds to a pseudo-spin singlet, which is selected by the inter-valley short-range Coulomb interaction. Single-electron excitation spectra and STM wave function images may validate this scenario, as shown by our numerical simulations.

Density functional theory for open-shell singlet biradicals

NASA Astrophysics Data System (ADS)

Gräfenstein, Jürgen; Kraka, Elfi; Cremer, Dieter

1998-05-01

The description of open-shell singlet (OSS) σ- π biradicals by density functional theory (DFT) requires at least a two-configurational (TC) or, in general, a MC-DFT approach, which bears many unsolved problems. These can be avoided by reformulating the TC description in the spirit of restricted open shell theory for singlets (ROSS) and developing an exchange-correlation functional for ROSS-DFT. ROSS-DFT turns out to lead to reliable descriptions of geometry and vibrational frequencies for OSS biradicals. The relative energies of the OSS states obtained at the ROSS-B3LYP/6-311G(d,p) level are often better than the corresponding ROSS-MP2 results. However, in those cases where spin polarization in a conjugated π systems plays a role, DFT predicts the triplet state related to the OSS state 2-4 kcal/mol too stable.

Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

DOE PAGES

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; ...

2016-05-18

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ CS = 161 ± 4 ps) in polar CH 2Cl 2, which is thermodynamically favored with a Gibbs free energy of ΔG CS = –0.32 eV. The charges then recombine slowly in τ CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events ismore » eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH 2Cl 2. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.« less

Promoting Singlet/triplet Exciton Transformation in Organic Optoelectronic Molecules: Role of Excited State Transition Configuration.

PubMed

Chen, Runfeng; Tang, Yuting; Wan, Yifang; Chen, Ting; Zheng, Chao; Qi, Yuanyuan; Cheng, Yuanfang; Huang, Wei

2017-07-24

Exciton transformation, a non-radiative process in changing the spin multiplicity of an exciton usually between singlet and triplet forms, has received much attention recently due to its crucial effects in manipulating optoelectronic properties for various applications. However, current understanding of exciton transformation mechanism does not extend far beyond a thermal equilibrium of two states with different multiplicity and it is a significant challenge to probe what exactly control the transformation between the highly active excited states. Here, based on the recent developments of three types of purely organic molecules capable of efficient spin-flipping, we perform ab initio structure/energy optimization and similarity/overlap extent analysis to theoretically explore the critical factors in controlling the transformation process of the excited states. The results suggest that the states having close energy levels and similar exciton characteristics with same transition configurations and high heteroatom participation are prone to facilitating exciton transformation. A basic guideline towards the molecular design of purely organic materials with facile exciton transformation ability is also proposed. Our discovery highlights systematically the critical importance of vertical transition configuration of excited states in promoting the singlet/triplet exciton transformation, making a key step forward in excited state tuning of purely organic optoelectronic materials.

Non-thermal leptogenesis with distinct CP violation and minimal dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hang; Gu, Pei-Hong, E-mail: einsteinzh@sjtu.edu.cn, E-mail: peihong.gu@sjtu.edu.cn

We demonstrate a unified scenario for neutrino mass, baryon asymmetry, dark matter and inflation. In addition to a fermion triplet for the so-called minimal dark matter, we extend the standard model by three heavy fields including a scalar singlet, a fermion triplet and a fermion singlet/Higgs triplet. The heavy scalar singlet, which is expected to drive an inflation, and the dark matter fermion triplet are odd under an unbroken Z {sub 2} discrete symmetry, while the other fields are all even. The heavy fermion triplet offers a tree-level type-III seesaw and then mediates a three-body decay of the inflaton intomore » the standard model lepton and Higgs doublets with the dark matter fermion triplet. The heavy fermion singlet/Higgs triplet not only results in a type-I/II seesaw at tree level but also contributes to the inflaton decay at one-loop level. In this scenario, the type-I/II seesaw contains all of the physical CP phases in the lepton sector and hence the CP violation for the non-thermal leptogenesis by the inflaton decay exactly comes from the imaginary part of the neutrino mass matrix.« less

Regulation of singlet oxygen-induced apoptosis by cytosolic NADP+-dependent isocitrate dehydrogenase.

PubMed

Kim, Sun Yee; Lee, Su Min; Tak, Jean Kyoung; Choi, Kyeong Sook; Kwon, Taeg Kyu; Park, Jeen-Woo

2007-08-01

Singlet oxygen is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules and it also promotes deleterious processes such as cell death. Recently, we demonstrated that the control of redox balance and the cellular defense against oxidative damage are the primary functions of cytosolic NADP(+)-dependent isocitrate dehydrogenase (IDPc) through supplying NADPH for antioxidant systems. In this report, we demonstrate that modulation of IDPc activity in HL-60 cells regulates singlet oxygen-induced apoptosis. When we examined the protective role of IDPc against singlet oxygen-induced apoptosis with HL-60 cells transfected with the cDNA for mouse IDPc in sense and antisense orientations, a clear inverse relationship was observed between the amount of IDPc expressed in target cells and their susceptibility to apoptosis. The results suggest that IDPc plays an important protective role in apoptosis of HL-60 cells induced by singlet oxygen.

Generalized-active-space pair-density functional theory: an efficient method to study large, strongly correlated, conjugated systems.

PubMed

Ghosh, Soumen; Cramer, Christopher J; Truhlar, Donald G; Gagliardi, Laura

2017-04-01

Predicting ground- and excited-state properties of open-shell organic molecules by electronic structure theory can be challenging because an accurate treatment has to correctly describe both static and dynamic electron correlation. Strongly correlated systems, i.e. , systems with near-degeneracy correlation effects, are particularly troublesome. Multiconfigurational wave function methods based on an active space are adequate in principle, but it is impractical to capture most of the dynamic correlation in these methods for systems characterized by many active electrons. We recently developed a new method called multiconfiguration pair-density functional theory (MC-PDFT), that combines the advantages of wave function theory and density functional theory to provide a more practical treatment of strongly correlated systems. Here we present calculations of the singlet-triplet gaps in oligoacenes ranging from naphthalene to dodecacene. Calculations were performed for unprecedently large orbitally optimized active spaces of 50 electrons in 50 orbitals, and we test a range of active spaces and active space partitions, including four kinds of frontier orbital partitions. We show that MC-PDFT can predict the singlet-triplet splittings for oligoacenes consistent with the best available and much more expensive methods, and indeed MC-PDFT may constitute the benchmark against which those other models should be compared, given the absence of experimental data.

Electronic Structure of Ethynyl Substituted Cyclobutadienes

NASA Astrophysics Data System (ADS)

Emmert, Frank Lee Emmert, III; Thompson, Stephanie J.; Slipchenko, Lyudmila V.

2011-06-01

We investigated the effects of ethynyl substitution on the electronic structure of cyclobutadiene. These species are involved in Bergman Cyclization reactionsand are possible intermediates in the formation of fullerenes and graphite sheets. Prediction of the electronic energy of cyclobutadiene is challenging for single-reference ab initio methods such as HF, MP2 or DFT because of Jahn-Teller distortions and the diradical character of the singlet state. We determined the vertical and adiabatic singlet-triplet energy splittings, the natural charges and spin densities in substituted cyclobutadienes, using the equations of motion spin flip coupled cluster with single and double excitations (EOM-SF-CCSD) method that accurately describes diradical states. The adiabatic singlet-triplet gaps decrease upon substituent addition, but the singlet state is always lower in energy. However, we found that the results are affected by spin-contamination of the reference state and deteriorate when an unrestricted HF reference is employed. O. L. Chapman, C. L. McIntosh, J. Pacansky, "Cyclobutadiene" J. Am. Chem. Soc. 1973, 95, (2), 614-617. N. S. Goroff, "Mechanism of Fullerene Formation." Acc. Chem. Res. 1996, 29, (2), 77-83. L.V. Slipchenko and A.I. Krylov, "Singlet-triplet gaps in diradicals by the Spin-Flip approach: A benchmark study", J. Chem. Phys. 2002, 117, 4694-4708.

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

NASA Astrophysics Data System (ADS)

Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

2015-12-01

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

Two-dimensional singlet oxygen imaging with its near-infrared luminescence during photosensitization

PubMed Central

Hu, Bolin; Zeng, Nan; Liu, Zhiyi; Ji, Yanhong; Xie, Weidong; Peng, Qing; Zhou, Yong; He, Yonghong; Ma, Hui

2011-01-01

Photodynamic therapy is a promising cancer treatment that involves activation of photosensitizer by visible light to create singlet oxygen. This highly reactive oxygen species is believed to induce cell death and tissue destruction in PDT. Our approach used a near-infrared area CCD with high quantum efficiency to detect singlet oxygen by its 1270-nm luminescence. Two-dimensional singlet oxygen images with its near-infrared luminescence during photosensitization could be obtained with a CCD integration time of 1 s, without scanning. Thus this system can produce singlet oxygen luminescence images faster and achieve more accurate measurements in comparison to raster-scanning methods. The experimental data show a linear relationship between the singlet oxygen luminescence intensity and sample concentration. This method provides a detection sensitivity of 0.0181 μg/ml (benzoporphyrin derivative monoacid ring A dissolved in ethanol) and a spatial resolution better than 50 μm. A pilot study was conducted on a total of six female Kunming mice. The results from this study demonstrate the system's potential for in vivo measurements. Further experiments were carried out on two tumor-bearing nude mice. Singlet oxygen luminescence images were acquired from the tumor-bearing nude mouse with intravenous injection of BPD-MA, and the experimental results showed real-time singlet oxygen signal depletion as a function of the light exposure. PMID:21280909

Computed Regioselectivity and Conjectured Biological Activity of Ene Reactions of Singlet Oxygen with the Natural Product Hyperforin.

PubMed

Abramova, Inna; Rudshteyn, Benjamin; Liebman, Joel F; Greer, Alexander

2017-03-01

Hyperforin is a constituent of St. John's wort and coexists with the singlet oxygen sensitizer hypericin. Density functional theory, molecular mechanics and Connolly surface calculations show that accessibility in the singlet oxygen "ene" reaction favors the hyperforin "southwest" and "southeast" prenyl (2-methyl-2-butenyl) groups over the northern prenyl groups. While the southern part of hyperforin is initially more susceptible to oxidation, up to 4 "ene" reactions of singlet oxygen can take place. Computational results assist in predicting the fate of adjacent hydroperoxides in hyperforin, where the loss of hydrogen atoms may lead to the formation of a hydrotrioxide and a carbonyl instead of a Russell reaction. © 2017 The American Society of Photobiology.

Theoretical studies of ground and excited electronic States in a series of rhenium(i) bipyridine complexes containing diarylethynyl-based structure.

PubMed

Yang, Li; Ren, Ai-Min; Feng, Ji-Kang; Liu, Xiao-Dong; Ma, Yu-Guang; Zhang, Hong-Xing

2004-09-20

The photophysical properties, which vary as X is varied, of Re(I)-halide complexes (X2-bpy)ReICl(CO)3 (where X=ph, DAE, DNE, and DPE; ph = phenyl (1); DAE = di(amineoethynylbenzene) (2); DPE = di(phenylethynylbenzene) (3); DNE = di(nitroethynylbenzene) (4); bpy=2,2'bipyridine), are investigated using density functional theory (DFT). The electronic properties of the neutral molecules, in addition to the positive and negative ions, are studied using B3LYP functional. Excited singlet and triplet states are examined using time-dependent density functional theory (TDDFT). The low-lying excited-state geometries are optimized at the ab initio configuration interaction singlets level. As shown, the diarylethynyl-based structure is an integral component of the bpy pi-conjugated network, which results in a good planar structure. The occupied orbitals involved in the transitions have a significant mixture of metal Re and group Cl, and the lowest unoccupied orbital is a pi orbital, which extends from ligand bpy to diarylethynyl-based substituents. The luminescence for each complex originates from the lowest triplet excited states and is assigned to the mixing of MLCT and LLCT characters. Significant insights on the effects of these diarylethynyl conjugated structure and ending substituents (NH2, ph, and NO2) on absorption and emission spectra are observed by analysis of the results of the TDDFT method. The diarylethynyl-based pi-conjugated network makes both the absorption and emission spectra red-shifted compared with simple complex (bpy)ReICl(CO)3. Furthermore, an electron-releasing group (NH2) makes absorption and emission spectra blue-shift and an electron-withdrawing group (NO2) makes them red-shift. Copyright 2004 American Chemical Society

Sizable NSI from the SU(2) L scalar doublet-singlet mixing and the implications in DUNE

DOE PAGES

Forero, David V.; Huang, Wei -Chih

2017-03-03

Here, we propose a novel and simple mechanism where sizable effects of non-standard interactions (NSI) in neutrino propagation are induced from the mixing between an electrophilic second Higgs doublet and a charged singlet. The mixing arises from a dimensionful coupling of the scalar doublet and singlet to the standard model Higgs boson. In light of the small mass, the light mass eigenstate from the doublet-singlet mixing can generate much larger NSI than those induced by the heavy eigenstate. We show that a sizable NSI ε eτ (~0.3) can be attained without being excluded by a variety of experimental constraints. Furthermore,more » we demonstrate that NSI can mimic effects of the Dirac CP phase in the neutrino mixing matrix but they can potentially be disentangled by future long-baseline neutrino experiments, such as the Deep Underground Neutrino Experiment (DUNE).« less

Spin-orbit signatures in the dynamics of singlet-triplet qubits in double quantum dots

NASA Astrophysics Data System (ADS)

Rolon, Juan E.; Cota, Ernesto; Ulloa, Sergio E.

2017-05-01

We characterize numerically and analytically the signatures of the spin-orbit interaction in a two-electron GaAs double quantum dot in the presence of an external magnetic field. In particular, we obtain the return probability of the singlet state by simulating Landau-Zener voltage detuning sweeps which traverse the singlet-triplet (S -T+ ) resonance. Our results indicate that non-spin-conserving interdot tunneling processes arising from the spin-orbit interaction have well defined signatures. These allow direct access to the spin-orbit interaction scales and are characterized by a frequency shift and Fourier amplitude modulation of the Rabi flopping dynamics of the singlet-triplet qubits S -T0 and S -T+ . By applying the Bloch-Feshbach projection formalism, we demonstrate analytically that the aforementioned effects originate from the interplay between spin-orbit interaction and processes driven by the hyperfine interaction between the electron spins and those of the GaAs nuclei.

Sizable NSI from the SU(2) L scalar doublet-singlet mixing and the implications in DUNE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Forero, David V.; Huang, Wei -Chih

Here, we propose a novel and simple mechanism where sizable effects of non-standard interactions (NSI) in neutrino propagation are induced from the mixing between an electrophilic second Higgs doublet and a charged singlet. The mixing arises from a dimensionful coupling of the scalar doublet and singlet to the standard model Higgs boson. In light of the small mass, the light mass eigenstate from the doublet-singlet mixing can generate much larger NSI than those induced by the heavy eigenstate. We show that a sizable NSI ε eτ (~0.3) can be attained without being excluded by a variety of experimental constraints. Furthermore,more » we demonstrate that NSI can mimic effects of the Dirac CP phase in the neutrino mixing matrix but they can potentially be disentangled by future long-baseline neutrino experiments, such as the Deep Underground Neutrino Experiment (DUNE).« less

Mn@Si14+: a singlet fullerene-like endohedrally doped silicon cluster.

PubMed

Ngan, Vu Thi; Pierloot, Kristine; Nguyen, Minh Tho

2013-04-21

The electronic structure of Mn@Si14(+) is determined using DFT and CASPT2/CASSCF(14,15) computations with large basis sets. The endohedrally Mn-doped Si cationic cluster has a D3h fullerene-like structure featuring a closed-shell singlet ground state with a singlet-triplet gap of ~1 eV. A strong stabilizing interaction occurs between the 3d(Mn) and the 2D-shell(Si14) orbitals, and a large amount of charge is transferred from the Si14 cage to the Mn dopant. The 3d(Mn) orbitals are filled by encapsulation, and the magnetic moment of Mn is completely quenched. Full occupation of [2S, 2P, 2D] shell orbitals by 18 delocalized electrons confers the doped Mn@Si14(+) cluster a spherically aromatic character.

Photophysics of covalently functionalized single wall carbon nanotubes with verteporfin

NASA Astrophysics Data System (ADS)

Staicu, Angela; Smarandache, Adriana; Pascu, Alexandru; Pascu, Mihail Lucian

2017-09-01

Covalently functionalized single wall carbon nanotubes (SWCNT) with the photosensitizer verteporfin (VP) were synthesized and studied. Photophysical properties of the obtained compounds like optical absorption, laser-induced fluorescence and generated singlet oxygen were investigated. In order to highlight the features of the conjugated compound, its photophysical characteristics were compared with those of the mixtures of the initial components. The optical absorption data evidenced a compound that combines features of the primary SWCNTs and VP. This is the also the case of the laser induced fluorescence of the synthesized product. Moreover, fluorescence quantum yield (Φf) of the compound (Φf = 2.4%) is smaller than for the mixture of SWCNT and VP in (Φf = 3.2%). The behavior is expected, because linked VP (carrying the fluorescent moiety) transfers easier a part of its excitation energy to the SWCNT in the covalent structure. Relative to the quantum yield of singlet oxygen generation (ΦΔ) by Methylene Blue, it was found that the ΦΔ for the conjugated VP-SWCNT is 51% while for the mixture ΦΔ is 23%. The results indicate covalently functionalized single walled carbon nanotubes with verteporfin as potential compounds of interest in targeted drug delivery and photodynamic therapy.

Kondo necklace model in approximants of Fibonacci chains

NASA Astrophysics Data System (ADS)

Reyes, Daniel; Tarazona, H.; Cuba-Supanta, G.; Landauro, C. V.; Espinoza, R.; Quispe-Marcatoma, J.

2017-11-01

The low energy behavior of the one dimensional Kondo necklace model with structural aperiodicity is studied using a representation for the localized and conduction electron spins, in terms of local Kondo singlet and triplet operators at zero temperature. A decoupling scheme on the double time Green's functions is used to find the dispersion relation for the excitations of the system. We determine the dependence between the structural aperiodicity modulation and the spin gap in a Fibonacci approximant chain at zero temperature and in the paramagnetic side of the phase diagram.

Intensity and temperature-dependent photoluminescence of tris (8-hydroxyquinoline) aluminum films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ajward, A. M.; Wang, X.; Wagner, H. P.

2013-12-04

We investigate the recombination of excitons in tris (8-hydroxyquinoline) aluminum films by intensity and temperature dependent time-resolved photoluminescence (PL). At low temperature (15 K) and elevated excitation intensity the radiative emission is quenched by singlet-singlet annihilation processes. With rising temperature the PL quenching is strongly reduced resulting in a PL efficiency maximum at ∼170 K. The reduced exciton annihilation is attributed to thermally activated occupation of non-quenchable trapped exciton states. Above 170 K the PL efficiency decreases due to thermal de-trapping of radiative states and subsequent migration to non-radiative centers.

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs.

PubMed

Nelson, Jordan N; Krzyaniak, Matthew D; Horwitz, Noah E; Rugg, Brandon K; Phelan, Brian T; Wasielewski, Michael R

2017-03-23

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m s = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet m s = 0 spin states are formally forbidden (Δm s = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Generalized One-Band Model Based on Zhang-Rice Singlets for Tetragonal CuO.

PubMed

Hamad, I J; Manuel, L O; Aligia, A A

2018-04-27

Tetragonal CuO (T-CuO) has attracted attention because of its structure similar to that of the cuprates. It has been recently proposed as a compound whose study can give an end to the long debate about the proper microscopic modeling for cuprates. In this work, we rigorously derive an effective one-band generalized t-J model for T-CuO, based on orthogonalized Zhang-Rice singlets, and make an estimative calculation of its parameters, based on previous ab initio calculations. By means of the self-consistent Born approximation, we then evaluate the spectral function and the quasiparticle dispersion for a single hole doped in antiferromagnetically ordered half filled T-CuO. Our predictions show very good agreement with angle-resolved photoemission spectra and with theoretical multiband results. We conclude that a generalized t-J model remains the minimal Hamiltonian for a correct description of single-hole dynamics in cuprates.

Generalized One-Band Model Based on Zhang-Rice Singlets for Tetragonal CuO

NASA Astrophysics Data System (ADS)

Hamad, I. J.; Manuel, L. O.; Aligia, A. A.

2018-04-01

Tetragonal CuO (T-CuO) has attracted attention because of its structure similar to that of the cuprates. It has been recently proposed as a compound whose study can give an end to the long debate about the proper microscopic modeling for cuprates. In this work, we rigorously derive an effective one-band generalized t -J model for T-CuO, based on orthogonalized Zhang-Rice singlets, and make an estimative calculation of its parameters, based on previous ab initio calculations. By means of the self-consistent Born approximation, we then evaluate the spectral function and the quasiparticle dispersion for a single hole doped in antiferromagnetically ordered half filled T-CuO. Our predictions show very good agreement with angle-resolved photoemission spectra and with theoretical multiband results. We conclude that a generalized t -J model remains the minimal Hamiltonian for a correct description of single-hole dynamics in cuprates.

Photodynamic Modification Of Plasma Membrane Function In Erythrocytes Sensitized By Xanthenes: What Determines Potency?

NASA Astrophysics Data System (ADS)

Pooler, John P.

1988-02-01

Several xanthene sensitizers were compared as sensitizers of membrane function in erythrocytes and some of their physico-chemical properties were examined. Eosin derivatives that localize at different membrane sites were equally effective at sensitizing both ion leaks and inactivation of membrane cholinesterase, implying that a diffusible intermediate reacts with membrane targets. Assessments of membrane loading and calculations of diffusion distances for singlet oxygen indicate that amounts of membrane-located sensitizer are quantitatively much greater than amounts in the nearby reaction medium. Potency measurements and assessment of absorption spectra and singlet oxygen production in water-dioxane mixtures lead to the conclusion that differential sorption to membranes, photon capture in low polarity environments and conversion of excited states to singlet oxygen are they key determinants of sensitizing potency.

Excitons and Davydov splitting in sexithiophene from first-principles many-body Green's function theory

NASA Astrophysics Data System (ADS)

Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen

2015-09-01

Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green's function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.

Higher Order π-Conjugated Polycyclic Hydrocarbons with Open-Shell Singlet Ground State: Nonazethrene versus Nonacene.

PubMed

Huang, Rui; Phan, Hoa; Herng, Tun Seng; Hu, Pan; Zeng, Wangdong; Dong, Shao-Qiang; Das, Soumyajit; Shen, Yongjia; Ding, Jun; Casanova, David; Wu, Jishan

2016-08-17

Higher order acenes (i.e., acenes longer than pentacene) and extended zethrenes (i.e., zethrenes longer than zethrene) are theoretically predicted to have an open-shell singlet ground state, and the radical character is supposed to increase with extension of molecular size. The increasing radical character makes the synthesis of long zethrenes and acenes very challenging, and so far, the longest reported zethrene and acene derivatives are octazethrene and nonacene, respectively. In addition, there is a lack of fundamental understanding of the differences between these two closely related open-shell singlet systems. In this work, we report the first synthesis of a challenging nonazethrene derivative, HR-NZ, and its full structural and physical characterizations including variable temperature NMR, ESR, SQUID, UV-vis-NIR absorption and electrochemical measurements. Compound HR-NZ has an open-shell singlet ground state with a moderate diradical character (y0 = 0.48 based on UCAM-B3LYP calculation) and a small singlet-triplet gap (ΔES-T = -5.2 kcal/mol based on SQUID data), thus showing magnetic activity at room temperature. It also shows amphoteric redox behavior, with a small electrochemical energy gap (1.33 eV). Its electronic structure and physical properties are compared with those of Anthony's nonacene derivative JA-NA and other zethrene derivatives. A more general comparison between higher order acenes and extended zethrenes was also conducted on the basis of ab initio electronic structure calculations, and it was found that zethrenes and acenes have very different spatial localization of the unpaired electrons. As a result, a faster decrease of singlet-triplet energy gap and a faster increase of radical character with increase of the number of benzenoid rings were observed in zethrene series. Our studies reveal that spatial localization of the frontier molecular orbitals play a very important role on the nature of radical character as well as the excitation energy.

Relaxed structure of typical nitro explosives in the excited state: Observation, implication and application

NASA Astrophysics Data System (ADS)

Chu, Genbai; Yang, Zuhua; Xi, Tao; Xin, Jianting; Zhao, Yongqiang; He, Weihua; Shui, Min; Gu, Yuqiu; Xiong, Ying; Xu, Tao

2018-04-01

Understanding the structural, geometrical, and chemical changes that occur after an electronic excitation is essential to elucidate the inherent mechanism of nitro explosives. Herein, relaxed structures of typical nitro explosives in the lowest singlet excited state are investigated using time-dependent density functional theory. During the excitation process, the nitro group is activated and relaxes via geometrical change. The five explosives RDX, HMX, CL-20, PETN, and LLM-105 exhibit similar relaxed structures, and the impact sensitivity is related to their excitation energy. High-sensitivity δ-HMX has a lower excitation energy for relaxed structure than β-HMX. This study offers novel insight into energetic materials.

Mass-improvement of the vector current in three-flavor QCD

NASA Astrophysics Data System (ADS)

Fritzsch, P.

2018-06-01

We determine two improvement coefficients which are relevant to cancel mass-dependent cutoff effects in correlation functions with operator insertions of the non-singlet local QCD vector current. This determination is based on degenerate three-flavor QCD simulations of non-perturbatively O( a) improved Wilson fermions with tree-level improved gauge action. Employing a very robust strategy that has been pioneered in the quenched approximation leads to an accurate estimate of a counterterm cancelling dynamical quark cutoff effects linear in the trace of the quark mass matrix. To our knowledge this is the first time that such an effect has been determined systematically with large significance.

Modeling the oxygen microheterogeneity of tumors for photodynamic therapy dosimetry

NASA Astrophysics Data System (ADS)

Pogue, Brian W.; Paulsen, Keith D.; O'Hara, Julia A.; Hoopes, P. Jack; Swartz, Harold

2000-03-01

Photodynamic theory of tumors uses optical excitation of a sensitizing drug within tissue to produce large deposits of singlet oxygen, which are thought to ultimately cause the tumor destruction. Predicting dose deposition of singlet oxygen in vivo is challenging because measurement of this species in vivo is not easily achieved. But it is possible to follow the concentration of oxygen in vivo, and so measuring the oxygen concentration transients during PDT may provide a viable method of estimating the delivered dose of singlet oxygen. However modeling the microscopic heterogeneity of the oxygen distribution within a tumor is non-trivial, and predicting the microscopic dose deposition requires further study, but this study present the framework and initial calibration needed or modeling oxygen transport in complex geometries. Computational modeling with finite elements provides a versatile structure within which oxygen diffusion and consumption can be modeled within realistic tissue geometries. This study develops the basic tools required to simulate a tumor region, and examines the role of (i) oxygen supply and consumption rates, (ii) inter- capillary spacing, (iii) photosensitizer distribution, and (iv) differences between simulated tumors and those derived directly from histology. The result of these calculations indicate that realistic tumor tissue capillary networks can be simulated using the finite element method, without excessive computational burden for 2D regions near 1 mm2, and 3D regions near 0.1mm3. These simulations can provide fundamental information about tissue and ways to implement appropriate oxygen measurements. These calculations suggest that photodynamic therapy produces the majority of singlet oxygen in and near the blood vessels, because these are the sites of highest oxygen tension. These calculations support the concept that tumor vascular regions are the major targets for PDT dose deposition.

Contrasting SYK-like models

NASA Astrophysics Data System (ADS)

Krishnan, Chethan; Pavan Kumar, K. V.; Rosa, Dario

2018-01-01

We contrast some aspects of various SYK-like models with large- N melonic behavior. First, we note that ungauged tensor models can exhibit symmetry breaking, even though these are 0+1 dimensional theories. Related to this, we show that when gauged, some of them admit no singlets, and are anomalous. The uncolored Majorana tensor model with even N is a simple case where gauge singlets can exist in the spectrum. We outline a strategy for solving for the singlet spectrum, taking advantage of the results in arXiv:1706.05364, and reproduce the singlet states expected in N = 2. In the second part of the paper, we contrast the random matrix aspects of some ungauged tensor models, the original SYK model, and a model due to Gross and Rosenhaus. The latter, even though disorder averaged, shows parallels with the Gurau-Witten model. In particular, the two models fall into identical Andreev ensembles as a function of N . In an appendix, we contrast the (expected) spectra of AdS2 quantum gravity, SYK and SYK-like tensor models, and the zeros of the Riemann Zeta function.

Effects of Visible Irradiation of Protoporphyrin IX on the Self Assembly of Tubulin Heterodimers

PubMed Central

Sagarra, Alicia Vall; McMicken, Brady; Nonell, Santi; Brancaleon, Lorenzo

2016-01-01

The formation and the effects of the laser irradiation of the complex formed by protoporphyrin IX (PPIX) and tubulin was investigated. We have used tubulin as a model protein to investigate whether docked photoactive ligands can affect the structure and function of polypeptides upon exposure to visible light. We observed that laser irradiation in the Soret band prompts bleaching of the PPIX which is accompanied by a sharp decrease in the intensity and average fluorescence lifetime of the protein (dominated by the four tryptophan residues of the tubulin monomer). The kinetics indicate non-trivial effects and suggest that the photosensitization of the PPIX bound to tubulin prompts structural alterations of the protein. These modifications were also observed through changes in the energy transfer between Trp residues and PPIX. The result suggest that laser irradiation produces localized partial unfolding of tubulin and that the changes prompt modification of the formation of microtubules in vitro. Measurements of singlet oxygen formation were inconclusive in determining whether the changes are prompted by reactive oxygen species or other excited state mechanisms. PMID:27490308

Electronic and ionization spectra of 1,1-diamino-2,2-dinitroethylene, FOX-7.

PubMed

Borges, Itamar

2014-03-01

Singlet, triplet and ionized states of the energetic molecule 1,1-diamino-2,2-dinitroethylene, known as FOX-7 or DADNE, were investigated using the symmetry-adapted-cluster configuration interaction (SAC-CI) ab initio wave function. The 20 computed singlet transitions, with 2 exceptions, were bright. The most intense singlet transitions were of the n₀→π type-typical of molecules having nitro groups. Fast intersystem crossing (ISC) from the 1¹A, 2¹A and 8¹A bright singlet transitions is possible. Other feasible ISC processes are discussed. The computed singlet and ionization spectra have similar features when compared to nitramide and N,N-dimethylnitramine molecules, which have only a nitro group. The ionization energies of the first 20 states have differences in comparison with Koopmans' energy values that can reach 3 eV. Moreover, the character of the first ionized states, dominated by single ionizations, is not the same when compared with the character resulting from application of Koopmans' theorem.

Solid-state, ambient-operation thermally activated delayed fluorescence from flexible, non-toxic gold-nanocluster thin films: towards the development of biocompatible light-emitting devices

NASA Astrophysics Data System (ADS)

Talite, M. J. A.; Lin, H. T.; Jiang, Z. C.; Lin, T. N.; Huang, H. Y.; Heredia, E.; Flores, A.; Chao, Y. C.; Shen, J. L.; Lin, C. A. J.; Yuan, C. T.

2016-08-01

Luminescent gold nanoclusters (AuNCs) with good biocompatibility have gained much attention in bio-photonics. In addition, they also exhibit a unique photo-physical property, namely thermally activated delayed fluorescence (TADF), by which both singlet and triplet excitons can be harvested. The combination of their non-toxic material property and unique TADF behavior makes AuNCs biocompatible nano-emitters for bio-related light-emitting devices. Unfortunately, the TADF emission is quenched when colloidal AuNCs are transferred to solid states under ambient environment. Here, a facile, low-cost and effective method was used to generate efficient and stable TADF emissions from solid AuNCs under ambient environment using polyvinyl alcohol as a solid matrix. To unravel the underlying mechanism, temperature-dependent static and transient photoluminescence measurements were performed and we found that two factors are crucial for solid TADF emission: small energy splitting between singlet and triplet states and the stabilization of the triplet states. Solid TADF films were also deposited on the flexible plastic substrate with patterned structures, thus mitigating the waveguide-mode losses. In addition, we also demonstrated that warm white light can be generated based on a co-doped single emissive layer, consisting of non-toxic, solution-processed TADF AuNCs and fluorescent carbon dots under UV excitation.

The 't Hooft vertex for staggered fermions and flavor-singlet mesons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donald, Gordon C.; Davies, Christine T.H.; Follana, Eduardo

2011-01-01

We derive the ’t Hooft vertex for staggered fermions and examine its symmetries for nonzero lattice spacing. We also derive a set of structural properties for the eigenvectors of the staggered Dirac operator, which should emerge in the continuum limit, if staggered fermions yield four species. This property also is needed for flavor-taste-singlet correlators to behave correctly. We then test numerically whether the needed structure arises: it does. This structure and symmetry of (unrooted) staggered fermions also imply that Creutz’s (latest) objections to the rooted determinant are without foundation.

(0,2) elephants

NASA Astrophysics Data System (ADS)

Aspinwall, Paul S.; Melnikov, Ilarion V.; Plesser, M. Ronen

2012-01-01

We enumerate massless E6 singlets for (0,2)-compactifications of the heterotic string on a Calabi-Yau threefold with the "standard embedding" in three distinct ways. In the large radius limit of the threefold, these singlets count deformations of the Calabi-Yau together with its tangent bundle. In the "small-radius" limit we apply Landau-Ginzburg methods. In the orbifold limit we use a combination of geometry and free field methods. In general these counts differ. We show how to identify states between these phases and how certain states vanish from the massless spectrum as one deforms the complex structure or Kähler form away from the Gepner point. The appearance of extra singlets for particular values of complex structure is explored in all three pictures, and our results suggest that this does not depend on the Kähler moduli.

Spin orbital singlet system FeSc2S4 under pressure

NASA Astrophysics Data System (ADS)

Biffin, Alun; Chernyshov, Dmitry; Canevet, Emmanuel; Fennell, Tom; White, Jonathan S.; Khasanov, Rustem; Luetkens, Hubertus; Loidl, Alois; Tsurkan, Vladimir; Rüegg, Christian

The role of orbital degrees of freedom in quantum magnets is receiving intense focus recently, with the understanding that spin-orbit coupled systems can display physics qualitatively different from their spin only counter parts. An example is the spin-orbital singlet (SOS) state, which can provide an alternative to the conventional spin and orbitally ordered groundstates of quantum magnets. In such a scenario, the relative strengths of the exchange interaction and spin orbit coupling parameters determine the low temperature structure, with the former preferring ordered moments and the latter a non-magnetic singlet. Moreover the quantum critical point separating these two phases is rather unique in that it marks the onset of criticality in both the spin and orbital sectors. This SOS picture has recently been applied to FeSc2S4, where despite strong antiferromagnetic exchange between Jahn-Teller active Fe2+ ions no experimental signature of spin or orbital order has been detected. Building on our previous neutron scattering measurements, we have used hydrostatic pressure in neutron scattering, muon spin rotation and x-ray diffraction measurements to probe the unique phase diagram of FeSc2S4. My talk will focus on the results and interpretation of these experiments SNF SCOPES project IZ73Z0_152734/1, the Marie Curie FP7 COFUND PSI Fellowship program, Swiss National Science Foundation.

The spectral properties of DNA and RNA macromolecules at low temperatures: fundamental and applied aspects

NASA Astrophysics Data System (ADS)

Yashchuk, Valeriy M.; Kudrya, Vladislav Yu

2017-03-01

This paper summarizes the results of studies of the spectral properties—optical absorption, fluorescence and phosphorescence—of DNA and RNA macromolecules and synthetic poly-, oligo- and mono-nucleotides, which have been carried out in our laboratory. The system of first excited singlet and triplet energy levels for DNA and RNA is evaluated using low-temperature (4.2 K-77 K) luminescent measurements. The traps of the singlet and triplet electronic excitations in these compounds are identified. An important self-protection mechanism against photo-damage of DNA and RNA by UV photons or penetrative radiation based on the capture of triplet electronic-energy excitations by the most photostable centers—in DNA, the complex formed by neighboring adenosine (A) and thymidine (T) links; in RNA, the adenosine links—is described. It is confirmed that despite similarities in the chemical and partly energy structures DNA is more stable than RNA. The spectral manifestation of the telomeres (the important functional system) in DNA macromolecules is examined. The results obtained on telomere fragments provide the possibility of finding the configuration peculiarities of the triplet excitations traps in DNA macromolecules. The resulting spreading length of the migrating singlet (l s) and triplet (l t) excitations for DNA and RNA macromolecules are evaluated.

Toward designed singlet fission: solution photophysics of two indirectly coupled covalent dimers of 1,3-diphenylisobenzofuran.

PubMed

Johnson, Justin C; Akdag, Akin; Zamadar, Matibur; Chen, Xudong; Schwerin, Andrew F; Paci, Irina; Smith, Millicent B; Havlas, Zdeněk; Miller, John R; Ratner, Mark A; Nozik, Arthur J; Michl, Josef

2013-04-25

In order to identify optimal conditions for singlet fission, we are examining the photophysics of 1,3-diphenylisobenzofuran (1) dimers covalently coupled in various ways. In the two dimers studied presently, the coupling is weak. The subunits are linked via the para position of one of the phenyl substituents, in one case (2) through a CH2 linker and in the other (3) directly, but with methyl substituents in ortho positions forcing a nearly perpendicular twist between the two joint phenyl rings. The measurements are accompanied with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Although in neat solid state, 1 undergoes singlet fission with a rate constant higher than 10(11) s(-1); in nonpolar solutions of 2 and 3, the triplet formation rate constant is less than 10(6) s(-1) and fluorescence is the only significant event following electronic excitation. In polar solvents, fluorescence is weaker because the initial excited singlet state S1 equilibrates by sub-nanosecond charge transfer with a nonemissive dipolar species in which a radical cation of 1 is attached to a radical anion of 1. Most of this charge transfer species decays to S0, and some is converted into triplet T1 with a rate constant near 10(8) s(-1). Experimental uncertainties prevent an accurate determination of the number of T1 excitations that result when a single S1 excitation changes into triplet excitation. It would be one if the charge-transfer species undergoes ordinary intersystem crossing and two if it undergoes the second step of two-step singlet fission. The triplet yield maximizes below room temperature to a value of roughly 9% for 3 and 4% for 2. Above ∼360 K, some of the S1 molecules of 3 are converted into an isomeric charge-transfer species with a shorter lifetime, possibly with a twisted intramolecular charge transfer (TICT) structure. This is not observed in 2.

Interaction of plasmalogens and their diacyl analogs with singlet oxygen in selected model systems

PubMed Central

Broniec, Agnieszka; Klosinski, Radoslaw; Pawlak, Anna; Wrona-Krol, Marta; Thompson, David; Sarna, Tadeusz

2011-01-01

Plasmalogens (Plg) are phospholipids containing vinyl ether linkage at the sn-1 position of the glycerophospholipid backbone. In spite of being quite abundant in humans, the biological role of plasmalogens remains speculative. It has been postulated that plasmalogens are physiological antioxidants with the vinyl ether functionality serving as sacrificial trap for free radicals and singlet oxygen. However, no quantitative data on the efficiency of plasmalogens to scavenge these reactive species are available. In this study, rate constants of quenching of singlet oxygen, generated by photosensitized energy transfer, by several plasmalogens and, for comparison, by their diacyl analogs, were determined by time-resolved detection of phosphorescence at 1270 nm. Relative rates of the interaction of singlet oxygen, with plasmalogens and other lipids in solution and liposomal membranes were measured by electron paramagnetic resonance oximetry and product analysis, employing HPLC-EC detection of cholesterol hydroperoxides and iodometric assay of lipid hydroperoxides. Results show that singlet oxygen interacts with plasmalogens significantly faster than with the other lipids, with he corresponding rate constants being by one-two orders of magnitude greater. The quenching of singlet oxygen by plasmalogens is mostly reactive in nature and results from its preferential interaction with the vinyl ether bond. The data suggest that plasmalogens could protect unsaturated membrane lipids against oxidation induced by singlet oxygen, providing that the oxidation products are not excessively cytotoxic. PMID:21236336

Flavor-singlet baryons in the graded symmetry approach to partially quenched QCD

NASA Astrophysics Data System (ADS)

Hall, Jonathan M. M.; Leinweber, Derek B.

2016-11-01

Progress in the calculation of the electromagnetic properties of baryon excitations in lattice QCD presents new challenges in the determination of sea-quark loop contributions to matrix elements. A reliable estimation of the sea-quark loop contributions represents a pressing issue in the accurate comparison of lattice QCD results with experiment. In this article, an extension of the graded symmetry approach to partially quenched QCD is presented, which builds on previous theory by explicitly including flavor-singlet baryons in its construction. The formalism takes into account the interactions among both octet and singlet baryons, octet mesons, and their ghost counterparts; the latter enables the isolation of the quark-flow disconnected sea-quark loop contributions. The introduction of flavor-singlet states enables systematic studies of the internal structure of Λ -baryon excitations in lattice QCD, including the topical Λ (1405 ).

Josephson effect in multiterminal superconductor-ferromagnet junctions coupled via triplet components

NASA Astrophysics Data System (ADS)

Moor, Andreas; Volkov, Anatoly F.; Efetov, Konstantin B.

2016-03-01

On the basis of the Usadel equation we study a multiterminal Josephson junction. This junction is composed by "magnetic" superconductors Sm, which have singlet pairing and are separated from the normal n wire by spin filters so that the Josephson coupling is caused only by fully polarized triplet components. We show that there is no interaction between triplet Cooper pairs with antiparallel total spin orientations. The presence of an additional singlet superconductor S attached to the n wire leads to a finite Josephson current IQ with an unusual current-phase relation. The density of states in the n wire for different orientations of spins of Cooper pairs is calculated. We derive a general formula for the current IQ in a multiterminal Josephson contact and apply this formula for analysis of two four-terminal Josephson junctions of different structures. It is shown in particular that both the "nematic" and the "magnetic" cases can be realized in these junctions. In a two-terminal structure with parallel filter orientations and in a three-terminal structure with antiparallel filter orientations of the "magnetic" superconductors with attached additional singlet superconductor, we find a nonmonotonic temperature dependence of the critical current. Also, in these structures, the critical current shows a Riedel peak like dependence on the exchange field in the "magnetic" superconductors. Although there is no current through the S/n interface due to orthogonality of the singlet and triplet components, the phase of the order parameter in the superconuctor S is shown to affect the Josephson current in a multiterminal structure.

Brightened spin-triplet interlayer excitons and optical selection rules in van der Waals heterobilayers

NASA Astrophysics Data System (ADS)

Yu, Hongyi; Liu, Gui-Bin; Yao, Wang

2018-07-01

We investigate the optical properties of spin-triplet interlayer excitons in heterobilayer transition metal dichalcogenides in comparison with the spin-singlet ones. Surprisingly, the optical transition dipole of the spin-triplet exciton is found to be in the same order of magnitude to that of the spin-singlet exciton, in sharp contrast to the monolayer excitons where the spin-triplet species is considered as dark compared to the singlet. Unlike the monolayer excitons whose spin-conserved (spin-flip) transition dipole can only couple to light of in-plane (out-of-plane) polarisation, such restriction is removed for the interlayer excitons due to the breaking of the out-of-plane mirror symmetry. We find that as the interlayer atomic registry changes, the optical transition dipole of interlayer exciton crosses between in-plane ones of opposite circular polarizations and the out-of-plane one for both the spin-triplet and spin-singlet species. As a result, excitons of both species have non-negligible coupling into photon modes of both in-plane and out-of-plane propagations, another sharp difference from the monolayers where the exciton couples predominantly into the out-of-plane propagation channel. At given atomic registry, the spin-triplet and spin-singlet excitons have distinct valley polarisation selection rules, allowing the selective optical addressing of both the valley configuration and the spin-singlet/triplet configuration of interlayer excitons.

Protection by Isoprene against Singlet Oxygen in Leaves

PubMed Central

Affek, Hagit P.; Yakir, Dan

2002-01-01

Isoprene (2-methyl-1,3-butadiene) protection against effects of singlet oxygen was investigated in Myrtus communis and Rhamnus alaternus. In M. communis, singlet oxygen produced in the leaves by Rose Bengal (RB) led to a 65% decrease in net assimilation rates within 3 h, whereas isoprene emission rates showed either a 30% decrease at ambient CO2 concentrations or a 70% increase under high CO2. In both cases, these changes led to an increase in calculated internal isoprene concentrations. The isoprene protection effect was directly demonstrated by fumigation of young (non-emitting) leaves, treated with RB or bromoxynil (simulating photoinhibition). There was 42% and 29% reduction in the damage to net assimilation compared with non-fumigated leaves for RB or bromoxynil, respectively. In R. alaternus, similar effects of RB on net assimilation were observed, and additional fluorescence measurements showed a significantly smaller decrease in Fv/Fm in isoprene-fumigated young leaves treated with RB (from 0.78 to 0.52), compared with non-fumigated leaves (from 0.77 to 0.27). The internal isoprene concentrations used in this study and possible rate of 1O2 production in leaves indicate that the protective effects observed should be beneficial also under natural conditions. PMID:12011357

Electronic structure and magnetic properties of disordered Co{sub 2}FeAl Heusler alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, Vishal, E-mail: vjain045@gmail.com; Jain, Vivek, E-mail: vjain045@gmail.com; Sudheesh, V. D., E-mail: vjain045@gmail.com

The effects of disorder on the magnetic properties of Co{sub 2}FeAl alloy are reported. X-ray diffraction exhibit A2-type disordered structure. Room temperature Mössbauer studies show the presence of two sextets with hyperfine field values of 31T and 30T along with a nonmagnetic singlet. The electronic structure of ordered and disordered Co{sub 2}FeAl alloys, investigated by means of the KKR Green's-function method shows that the magnetic moment of the ordered structure is 5.08μ{sub B} and is 5.10μ{sub B} when disordered. However, a much higher magnetic moment of 5.74μ{sub B} is observed experimentally.

Twisted Cyanines: A Non-Planar Fluorogenic Dye with Superior Photostability and its Use in a Protein-Based Fluoromodule

PubMed Central

Shank, Nathaniel I.; Pham, Ha; Waggoner, Alan S.; Armitage, Bruce A.

2013-01-01

The cyanine dye thiazole orange (TO) is a well-known fluorogenic stain for DNA and RNA, but this property precludes its use as an intracellular fluorescent probe for non-nucleic acid biomolecules. Further, as is the case with many cyanines, the dye suffers from low photostability. Here we report the synthesis of a bridge-substituted version of TO named α-CN-TO, where the central methine hydrogen of TO is replaced by an electron withdrawing cyano group, which was expected to decrease the susceptibility of the dye toward singlet oxygen-mediated degradation. An X-ray crystal structure shows that α-CN-TO is twisted drastically out of plane, in contrast to TO, which crystallizes in the planar conformation. α-CN-TO retains the fluorogenic behavior of the parent dye TO in viscous glycerol/water solvent, but direct irradiation and indirect bleaching studies showed that α-CN-TO is essentially inert to visible light and singlet oxygen. In addition, the twisted conformation of α-CN-TO mitigates non-specific binding and fluorescence activation by DNA and a previously selected TO-binding protein and exhibits low background fluorescence in HeLa cell culture. α-CN-TO was then used to select a new protein that binds and activates fluorescence from the dye. The new α-CN-TO/protein fluoromodule exhibits superior photostability to an analogous TO/protein fluoromodule. These properties indicate that α-CN-TO will be a useful fluorogenic dye in combination with specific RNA and protein binding partners for both in vitro and cell-based applications. More broadly, structural features that promote nonplanar conformations can provide an effective method for reducing nonspecific binding of cationic dyes to nucleic acids and other biomolecules. PMID:23252842

Structural fluctuation governed dynamic diradical character in pentacene.

PubMed

Yang, Hongfang; Chen, Mengzhen; Song, Xinyu; Bu, Yuxiang

2015-06-07

We unravel intriguing dynamical diradical behavior governed by structural fluctuation in pentacene using ab initio molecular dynamics simulation. In contrast to static equilibrium configuration of pentacene with a closed-shell ground state without diradical character, due to structural fluctuation, some of its dynamical snapshot configurations exhibit an open-shell broken-symmetry singlet ground state with diradical character, and such diradical character presents irregular pulsing behavior in time evolution. Not all structural changes can lead to diradical character, only those involving the shortening of cross-linking C-C bonds and variations of the C-C bonds in polyacetylene chains are the main contributors. This scenario about diradicalization is distinctly different from that in long acenes. The essence is that structural distortion cooperatively raises the HOMO and lowers the LUMO, efficiently reducing the HOMO-LUMO and singlet-triplet energy gaps, which facilitate the formation of a broken-symmetry open-shell singlet state. The irregular pulsing behavior originates from the mixing of normal vibrations in pentacene. This fascinating behavior suggests the potential application of pentacene as a suitable building block in the design of new electronic devices due to its magnetism-controllability through energy induction. This work provides new insight into inherent electronic property fluctuation in acenes.

Energetic Diagrams and Structural Properties of Monohaloacetylenes HC≡CX (X = F, Cl, Br).

PubMed

Khiri, D; Hochlaf, M; Chambaud, G

2016-08-04

Highly correlated electronic wave functions within the Multi Reference Configuration Interaction (MRCI) approach are used to study the stability and the formation processes of the monohaloacetylenes HCCX and monohalovinylidenes C2HX (X = F, Cl, Br) in their electronic ground state. These tetra-atomics can be formed through the reaction of triatomic fragments C2F, C2Cl, and C2Br with a hydrogen atom or of C2H with halogen atoms via barrierless reactions, whereas the reactions between the diatomics [C2 + HX] need to overcome barriers of 1.70, 0.89, and 0.58 eV for X = F, Cl, and Br. It is found that the linear HCCX isomers, in singlet symmetry, are more stable than the singlet C2HX iso-forms by 1.995, 2.083, and 1.958 eV for X = F, Cl, and Br. The very small isomerization barriers from iso to linear forms are calculated 0.067, 0.044, and 0.100 eV for F, Cl, and Br systems. The dissociation energies of the HCCX systems (without ZPE corrections), resulting from the breaking of the CX bond, are calculated to be 5.647, 4.691, and 4.129 eV for X = F, Cl, Br, respectively. At the equilibrium geometry of the X(1)Σ(+) state of HCCX, the vertical excitation energies in singlet and triplet symmetries are all larger than the respective dissociation energies. Stable excited states are found only as (3)A', (3)A″, and (1)A″ monohalovinylidene structures.

A well-scaling natural orbital theory

DOE PAGES

Gebauer, Ralph; Cohen, Morrel H.; Car, Roberto

2016-11-01

Here, we introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree–Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals ofmore » the oneparticle density matrix.« less

A well-scaling natural orbital theory

PubMed Central

Gebauer, Ralph; Cohen, Morrel H.; Car, Roberto

2016-01-01

We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree–Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals of the one-particle density matrix. PMID:27803328

Accurate adiabatic singlet-triplet gaps in atoms and molecules employing the third-order spin-flip algebraic diagrammatic construction scheme for the polarization propagator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lefrancois, Daniel; Dreuw, Andreas, E-mail: dreuw@uni-heidelberg.de; Rehn, Dirk R.

For the calculation of adiabatic singlet-triplet gaps (STG) in diradicaloid systems the spin-flip (SF) variant of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator in third order perturbation theory (SF-ADC(3)) has been applied. Due to the methodology of the SF approach the singlet and triplet states are treated on an equal footing since they are part of the same determinant subspace. This leads to a systematically more accurate description of, e.g., diradicaloid systems than with the corresponding non-SF single-reference methods. Furthermore, using analytical excited state gradients at ADC(3) level, geometry optimizations of the singlet and triplet states weremore » performed leading to a fully consistent description of the systems, leading to only small errors in the calculated STGs ranging between 0.6 and 2.4 kcal/mol with respect to experimental references.« less

Exact wave functions of two-electron quantum rings.

PubMed

Loos, Pierre-François; Gill, Peter M W

2012-02-24

We demonstrate that the Schrödinger equation for two electrons on a ring, which is the usual paradigm to model quantum rings, is solvable in closed form for particular values of the radius. We show that both polynomial and irrational solutions can be found for any value of the angular momentum and that the singlet and triplet manifolds, which are degenerate, have distinct geometric phases. We also study the nodal structure associated with these two-electron states.

Quintet multiexciton dynamics in singlet fission

DOE PAGES

Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango; ...

2016-10-17

Singlet fission, in which two triplet excitons are generated from a single absorbed photon, is a key third-generation solar cell concept. Conservation of angular momentum requires that singlet fission populates correlated multiexciton states, which can subsequently dissociate to generate free triplets. However, little is known about electronic and spin correlations in these systems since, due to its typically short lifetime, the multiexciton state is challenging to isolate and study. Here, we use bridged pentacene dimers, which undergo intramolecular singlet fission while isolated in solution and in solid matrices, as a unimolecular model system that can trap long-lived multiexciton states. Wemore » also combine transient absorption and time-resolved electron spin resonance spectroscopies to show that spin correlations in the multiexciton state persist for hundreds of nanoseconds. Furthermore, we confirm long-standing predictions that singlet fission produces triplet pair states of quintet character. Finally, we compare two different pentacene–bridge–pentacene chromophores, systematically tuning the coupling between the pentacenes to understand how differences in molecular structure affect the population and dissociation of multiexciton quintet states.« less

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Generation of singlet oxygen in fullerene-containing media: 2. Fullerene-containing solutions

NASA Astrophysics Data System (ADS)

Bagrov, I. V.; Belousova, I. M.; Grenishin, A. S.; Danilov, O. B.; Ermakov, A. V.; Kiselev, V. M.; Kislyakov, I. M.; Murav'eva, T. D.; Sosnov, E. N.

2008-03-01

The generation of singlet oxygen in fullerene solutions is studied by luminescence methods upon excitation by pulsed, repetitively pulsed, and continuous radiation sources. The concentration of singlet oxygen in solutions is measured in stationary and pulsed irradiation regimes. The rate constants of quenching of O2(1Δg) by fullerenes C70 and C60 in the CCl4 solution are measured to be (7.2±0.1)×107 L mol-1 s-1 and less than 6×104 L mol-1 s-1, respectively. The temperature and photolytic variations in the generation properties of the fullerene solution exposed to intense continuous radiation are studied by the methods of optical and EPR spectroscopy. Pulsed irradiation resulted in the production of singlet oxygen in suspensions of fullerene-like structures, in particular, astralenes. A liquid pulsed singlet-oxygen generator based on the fullerene solution in CCl4 is developed and studied, in which the yield of O2 (1Δg) to the gas phase at concentrations up to 5×1016 cm-3 is obtained.

1-Pentyl-3-(4-methoxy-1-naphthoyl)indole and 2-(2-methoxy-phenyl)-1-(1-pentyl-1 H-indol-3-yl)-ethanone: X-ray structures and computational studies

NASA Astrophysics Data System (ADS)

Nycz, Jacek E.; Malecki, Grzegorz; Zawiazalec, Marcin; Pazdziorek, Tadeusz; Skop, Patrycja

2010-12-01

1-Pentyl-3-(4-methoxy-1-naphthoyl)indole (shortly named JWH-081) ( 1) and 2-(2-methoxy-phenyl)-1-(1-pentyl-1 H-indol-3-yl)-ethanone (shortly named JWH-250) ( 2), are examples of cannabinoids which were characterized by FTIR, UV-Vis, multinuclear NMR spectroscopy and single crystal X-ray diffraction method. The geometries of the studied compounds were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. Electronic spectra were calculated by TDDFT method. In general, the predicted bond lengths and angles are in a good agreement with the values based on the X-ray crystal structure data.

Exposure of vitamins to UVB and UVA radiation generates singlet oxygen.

PubMed

Knak, Alena; Regensburger, Johannes; Maisch, Tim; Bäumler, Wolfgang

2014-05-01

Deleterious effects of UV radiation in tissue are usually attributed to different mechanisms. Absorption of UVB radiation in cell constituents like DNA causes photochemical reactions. Absorption of UVA radiation in endogenous photosensitizers like vitamins generates singlet oxygen via photosensitized reactions. We investigated two further mechanisms that might be involved in UV mediated cell tissue damage. Firstly, UVB radiation and vitamins also generate singlet oxygen. Secondly, UVB radiation may change the chemical structure of vitamins that may change the role of such endogenous photosensitizers in UVA mediated mechanisms. Vitamins were irradiated in solution using monochromatic UVB (308 nm) or UVA (330, 355, or 370 nm) radiation. Singlet oxygen was directly detected and quantified by its luminescence at 1270 nm. All investigated molecules generated singlet oxygen with a quantum yield ranging from 0.007 (vitamin D3) to 0.64 (nicotinamide) independent of the excitation wavelength. Moreover, pre-irradiation of vitamins with UVB changed their absorption in the UVB and UVA spectral range. Subsequently, molecules such as vitamin E and vitamin K1, which normally exhibit no singlet oxygen generation in the UVA, now produce singlet oxygen when exposed to UVA at 355 nm. This interplay of different UV sources is inevitable when applying serial or parallel irradiation with UVA and UVB in experiments in vitro. These results should be of particular importance for parallel irradiation with UVA and UVB in vivo, e.g. when exposing the skin to solar radiation.

Comparative study of singlet oxygen production by photosensitiser dyes encapsulated in silicone: towards rational design of anti-microbial surfaces.

PubMed

Noimark, Sacha; Salvadori, Enrico; Gómez-Bombarelli, Rafael; MacRobert, Alexander J; Parkin, Ivan P; Kay, Christopher W M

2016-10-12

Surfaces with built-in antimicrobial activity have the potential to reduce hospital-acquired infections. One promising strategy is to create functionalised surfaces which, following illumination with visible light, are able to generate singlet oxygen under aerobic conditions. In contrast to antibiotics, the mechanism of bacterial kill by species derived from reactions with singlet oxygen is completely unselective, therefore offering little room for evolutionary adaptation. Here we consider five commercially available organic photosensitiser dyes encapsulated in silicone polymer that show varied antimicrobial activity. We correlate density functional theory calculations with UV-Vis spectroscopy, electron paramagnetic resonance spectroscopy and singlet oxygen production measurements in order to define and test the elements required for efficacious antimicrobial activity. Our approach forms the basis for the rational in silico design and spectroscopic screening of simple and efficient self-sterilising surfaces made from cheap, low toxicity photosensitiser dyes encapsulated in silicone.

Carbon dioxide photolysis from 150 to 210 nm: singlet and triplet channel dynamics, UV-spectrum, and isotope effects.

PubMed

Schmidt, Johan A; Johnson, Matthew S; Schinke, Reinhard

2013-10-29

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ~167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ~0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues ((12)C(16)O2, (12)C(17)O(16)O, (12)C(18)O(16)O, (13)C(16)O2, and (13)C(18)O(16)O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of (17)O containing CO2 more efficient.

Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects

PubMed Central

Schmidt, Johan A.; Johnson, Matthew S.; Schinke, Reinhard

2013-01-01

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ∼167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ∼0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues (12C16O2, 12C17O16O, 12C18O16O, 13C16O2, and 13C18O16O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of 17O containing CO2 more efficient. PMID:23776249

Cytotoxicity But No Mutagenicity In Bacteria With Externally Generated Singlet Oxygen

NASA Astrophysics Data System (ADS)

Midden, W. Robert; Dahl, Thomas A.; Hartman, Philip E.

1988-02-01

Singlet oxygen is believed to be an important intermediate responsible for the cytotoxicity of HpD phototherapy. It has been recognized as a possible intermediate in photosensitization for more than 20 years. However, it has been difficult to obtain conclusive evidence of its biological characteristics in the past because most of the methods available for its generation that are compatible with biological systems also generate other reactive intermediates whose effects are difficult to distinguish from singlet oxygen. We have used a recently devised separated-surface-sensi-tizer (S-S-S) system for singlet oxygen generation' to measure the cytotoxicity and mutagenicity of singlet oxygen in bacteria. The S-S-S system employs rose bengal as a sensitizer immobilized on one surface of a glass plate. The glass plate is placed sensitizer-side down a small distance (< 1.5 mm) above a microscopically flat membrane (MilliporeTM or NucleoporeTM) that carries a monocellular layer of bacteria. The sensi-tizer-coated plate is illuminated from above to generate singlet oxygen at the surface of the sensitizer. The singlet oxygen thus generated can diffuse the short dis-tance to the surface of the membrane to react with the bacteria. Because of the short lifetime of singlet oxygen in air, increasing the distance between the sensitizer and the membrane causes a decline in the amount of singlet oxygen reaching the membrane according to a function derived from the Einstein-Smoluchowski equation for net displacement by diffusion. Plotting the log of the effect measured (e.g., cytotoxicity) vs. the square of the distance gives a straight line. The slope of this line can be used to calculate the gas phase half life of the intermediate responsible for the observed effects. We have found that bacteria are rapidly killed in the illuminated S-S-S system and that the gas phase half life of the agent responsible for cell killing is the same as that of singlet oxygen. This observation and other simple chemical tests have conclusively estab-lished that singlet oxygen is responsible for the cytotoxicity observed with bacteria. Dosimetry measurements allow us to estimate that singlet oxygen is at least 104 times more potent as a cytotoxin for Salmonella bacteria than hydrogen peroxide, on a molar basis. We have not observed mutagenicity in these bacteria exposed to sufficient singlet oxygen to kill 60-90% using a variety of bacterial strains and assays.

Anomaly-free dark matter models are not so simple

NASA Astrophysics Data System (ADS)

Ellis, John; Fairbairn, Malcolm; Tunney, Patrick

2017-08-01

We explore the anomaly-cancellation constraints on simplified dark matter (DM) models with an extra U(1)' gauge boson Z '. We show that, if the Standard Model (SM) fermions are supplemented by a single DM fermion χ that is a singlet of the SM gauge group, and the SM quarks have non-zero U(1)' charges, the SM leptons must also have non-zero U(1)' charges, in which case LHC searches impose strong constraints on the Z ' mass. Moreover, the DM fermion χ must have a vector-like U(1)' coupling. If one requires the DM particle to have a purely axial U(1)' coupling, which would be the case if χ were a Majorana fermion and would reduce the impact of direct DM searches, the simplest possibility is that it is accompanied by one other new singlet fermion, but in this case the U(1)' charges of the SM leptons still do not vanish. This is also true in a range of models with multiple new singlet fermions with identical charges. Searching for a leptophobic model, we then introduce extra fermions that transform non-trivially under the SM gauge group. We find several such models if the DM fermion is accompanied by two or more other new fermions with non-identical charges, which may have interesting experimental signatures. We present benchmark representatives of the various model classes we discuss.

Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study

DOE PAGES

Liu, Jin; Adamska, Lyudmyla; Doorn, Stephen K.; ...

2015-05-14

Conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid Density Functional Theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication.more » This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electron–phonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.« less

Computation of geometries and frequencies of singlet and triplet nitromethane with density functional theory byusing gaussian type orbitals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jursic, B.S.

1996-12-31

The results of the computational study of the structures, energies, dipole moments and IR spectra for a singlet and a triplet nitromethane are presented. Five different hybrids (BHandH, BHandHLYP, B3LYP, B3P86 and B3PW91), local (SVWN), and nonlocal (BLYP) DFT methods are used with various sizes of the gaussian type of basis set. The obtained results are compared to the HF, MP2, and MCSCF ab initio calculations, as well as, to the experimental results. Becke`s three functional based hybrid DFT methods outperform the following: the ab initio (HF, MP2 and MCSCF), the Becke`s half-and-half based DFT methods, and the local (SVWNmore » or LSDA) and nonlocal (BLYP) DFT methods. The computed nitromethane geometry, the dipole moment, the energy difference, and the IR frequency are in extraordinary agreement with the experimental results. Thus, we are recommending the B3LYP and the B3PW91 as the methods of choice when the computational study of small {open_quotes}difficult{close_quotes} molecules is considered.« less

Luminescence spectroscopic observation of singlet oxygen formation in extra virgin olive oil as affected by irradiation light wavelengths, 1,4-diazabicyclo[2.2.2]octane, irradiation time, and oxygen bubbling.

PubMed

Jung, Mun Y; Choi, Dong S; Park, Ki H; Lee, Bosoon; Min, David B

2011-01-01

A spectrofluorometer equipped with a highly sensitive near-IR InGaAs detector was used for the direct visualization of singlet oxygen emission at 1268 nm in olive oil during light irradiation with various different wavelengths. The virgin olive oil in methylene chloride (20% w/v, oxygen saturated) was irradiated at the 301, 417, 454, 483, and 668 nm, then the emission at 1268 nm, singlet oxygen dimole decaying was observed. The result showed the highest production of (1)O(2) with light irradiation at 417 nm, and followed by at 668 nm in virgin olive oil, indicating that pheophytin a and chlorophyll a were the most responsible components for the production of singlet oxygen. The UV light irradiations at the wavelength of 200, 250, and 300 nm did not induce any detectable luminescence emission at 1268 nm, but 350 nm produced weak emission at 1269 nm. The quantity of (1)O(2) produced with excitation at 350 nm was about 1/6 of that of irradiation at 417 nm. Addition of an efficient (1)O(2) quencher, 1,4-diazabicyclo[2.2.2]octane, in virgin olive oil in methylene chloride greatly decreased the luminescence emission at 1268 nm, confirming the singlet oxygen production in olive oil. Singlet oxygen production was more efficient in oxygen-purged virgin olive oil than in oxygen non-purged olive oil. This represents first report on the direct observation of singlet oxygen formation in olive oil as well as in real-food system after visible light illumination. Practical Application: The present results show the positive evidence of the singlet oxygen involvement in rapid oxidative deterioration of virgin olive oil under visible light. This paper also shows the effects of different wavelength of light irradiation on the formation of singlet oxygen in olive oil. The present results would provide important information for the understanding of the mechanism involved in rapid oxidative quality deterioration of virgin olive oil under light illumination and for searching the preventive methods of deterioration of olive oil quality under light.

Stability of the guanine endoperoxide intermediate: a computational challenge for density functional theory.

PubMed

Grüber, Raymond; Monari, Antonio; Dumont, Elise

2014-12-11

The addition of singlet molecular oxygen (1)O2 onto guanine is a most important and deleterious reaction in biological damage. We assess the efficiency of density functional theory for evaluating the respective stabilities of two intermediates that can form upon (1)O2 addition: a charge-separated adduct with a peroxide anion at the C8 position of guanine, and the corresponding cyclic endoperoxide across the 4,8-bond, of the imidazole ring. The reference post Hartree-Fock SCS-MP3/aug-cc-pVTZ//MP2/DZP++ level of theory provides an unambiguous assignment in favor of the endoperoxide intermediate, based on implicitly solvated structures, by -8.0 kcal·mol(-1). This value is taken as the reference for a systematic and extended benchmarck performed on 58 exchange--correlation functionals. While B3LYP remains commonly used for studying oxidative DNA lesions, we prove that the stability of the peroxide anion is overestimated by this functional, but also by other commonly used exchange-correlation functionals. The significant error (ca. +3 kcal·mol(-1) over a representative set of 58 functionals) arises from overdelocalization but also from the description of the dynamic correlation by the density functional. The significantly improved performance of several recently proposed functionals, including range-separated hybrids such as LC-BLYP, is outlined. We believe that our results will be of great help to further studies on the versatile chemistry of singlet oxygen-induced DNA damage, where complex reaction mechanisms are required to be depicted at a quantum level.

DFT calculations on molecular structure, spectral analysis, multiple interactions, reactivity, NLO property and molecular docking study of flavanol-2,4-dinitrophenylhydrazone

NASA Astrophysics Data System (ADS)

Singh, Ravindra Kumar; Singh, Ashok Kumar

2017-02-01

A new flavanol-2,4-dinitrophenylhydrazone (FDNP) was synthesized and its structure was confirmed by FT-IR, FT-Raman, 1H NMR, mass spectrometry and elemental analysis. All quantum chemical calculations were carried out at level of density functional theory (DFT) with B3LYP functional using 6-311++ G (d,p) basis atomic set. UV-Vis absorption spectra for the singlet-singlet transition computed for fully optimized ground state geometry using Time-Dependent-Density Functional Theory (TD-DFT) with CAM-B3LYP functional was found to be in consistent with that of experimental findings. Analysis of vibrational (FT-IR and FT-Raman) spectrum and their assignments has been done by computing Potential Energy Distribution (PED) using Gar2ped. HOMO-LUMO analysis was performed and reactivity descriptors were calculated. Calculated global electrophilicity index (ω = 7.986 eV) shows molecule to be a strong electrophile. 1H NMR chemical shift calculated with the help of gauge-including atomic orbital (GIAO) approach shows agreement with experimental data. Various intramolecular interactions were analysed by AIM approach. DFT computed total first static hyperpolarizability (β0 = 189.03 × 10-30 esu) indicates that title molecule can be used as attractive future NLO material. Solvent induced effects on the NLO properties studied by using self-consistent reaction field (SCRF) method shows that β0 value increases with increase in solvent polarity. To study the thermal behaviour of title molecule, thermodynamic properties such as heat capacity, entropy and enthalpy change at various temperatures have been calculated and reported. Molecular docking results suggests title molecule to be a potential kinase inhibitor and might be used in future for designing of new anticancer drug.

Variable charge transfer state energies at nanostructured pentacene/C60 interfaces

NASA Astrophysics Data System (ADS)

Lin, YunHui L.; Zhang, Fengyu; Kerner, Ross A.; Yang, Terry Chien-Jen; Kahn, Antoine; Rand, Barry P.

2018-05-01

While it has recently been recognized that organic donor-acceptor charge transfer (CT) state energies can vary substantially under different interfacial morphologies, this behavior is under-appreciated in the context of organic singlet fission solar cells where a specific alignment between the triplet state of the fission material and the CT state of the donor-acceptor interface is necessary to the function of the device. In this work, we demonstrate that the CT state energy of a prototypical pentacene-C60 singlet fission system is around 1 eV in most systems, but can vary over 300 meV depending on the composition and morphology of the interface. Moreover, we show that the inclusion of a poly(3-hexylthiophene-2,5-diyl) underlayer, which commonly serves as a triplet blocker and hole collector in pentacene/C60 solar cells, helps promote active layer morphologies with stabilized, low energy CT states. These trends in the interfacial energetics are correlated with structural characterization of the films by atomic force microscopy and x-ray diffraction.

Bright and dark singlet excitons via linear and two-photon spectroscopy in monolayer transition metal dichalcogenides

DOE PAGES

Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichmann, David R.

2015-08-10

We discuss the linear and two-photon spectroscopic selection rules for spin-singlet excitons in monolayer transition-metal dichalcogenides. Our microscopic formalism combines a fully k-dependent few-orbital band structure with a many-body Bethe-Salpeter equation treatment of the electron-hole interaction, using a model dielectric function. We show analytically and numerically that the single-particle, valley-dependent selection rules are preserved in the presence of excitonic effects. Furthermore, we definitively demonstrate that the bright (one-photon allowed) excitons have s-type azimuthal symmetry and that dark p-type excitons can be probed via two-photon spectroscopy. Thus, the screened Coulomb interaction in these materials substantially deviates from the 1/ε₀r form; thismore » breaks the “accidental” angular momentum degeneracy in the exciton spectrum, such that the 2p exciton has a lower energy than the 2s exciton by at least 50 meV. We compare our calculated two-photon absorption spectra to recent experimental measurements.« less

Two-Photon Absorption in Pentacene Dimers: The Importance of the Spacer Using Upconversion as an Indirect Route to Singlet Fission.

PubMed

Garoni, Eleonora; Zirzlmeier, Johannes; Basel, Bettina S; Hetzer, Constantin; Kamada, Kenji; Guldi, Dirk M; Tykwinski, Rik R

2017-10-11

In this proof of concept study, we show that intramolecular singlet fission (iSF) can be initiated from a singlet excited state accessed by two-photon absorption, rather than through a traditional route of direct one-photon excitation (OPE). Thus, iSF in pentacene dimers 2 and 3 is enabled through NIR irradiation at 775 nm, a wavelength where neither dimer exhibits linear absorption of light. The adamantyl and meta-phenylene spacers 2 and 3, respectively, are designed to feature superimposable geometries, which establishes that the electronic coupling between the two pentacenes is the significant structural feature that dictates iSF efficiency.

Trap formation and energy transfer in pheophorbide a-DAB-dendrimers and pyropheophorbide a-fullerene C 60 hexaadduct molecular systems

NASA Astrophysics Data System (ADS)

Röder, Beate; Ermilov, Eugeny A.; Hackbarth, Steffen; Helmreich, Matthias; Jux, Norbert

2006-04-01

The photophysical properties of DAB-dendrimers from 1 st to 4 th generation as well as Diaminohexane - all substituted with the in maximum achievable quantity of pheophorbide a (Pheo) molecules were studied in comparison with a novel hexapyropheophorbide a - fullerene hexaadduct (FHP6) and a fullerene [6:0]-hexaadduct which carries twelve pyropheophorbide a units (FHP12) using both steady-state and time-resolved spectroscopic methods. It was found that neighboring dye molecules covalently linked to one DAB- or fullerene moiety due to the length and high flexibility of carbon chains could stack with each other. This structural property is the reason for the possibility of formation different types of energy traps, which were resolved experimentally. The dipole-dipole resonance Förster energy transfer between the dye molecules coupled to one complex caused a very fast and efficient delivery of the excitation to a trap. As result the fluorescence as well as the singlet oxygen quantum yields of the different complexes were reduced with increasing number of dye molecules per complex. Nevertheless in every case the singlet oxygen generation was less influenced then the fluorescence quantum yield, exposing the complex to a non-negligible amount of excited oxygen in the singlet state. While the fullerene complexes turned out to be stable under these conditions, the DAB-dendrimer-backbones were completely fragmented to small rudiments carrying just one or a small number of dye molecules.

Re-examination of the Cs2 ground singlet X1Σg+ and triplet a3Σu+ states

NASA Astrophysics Data System (ADS)

Sovkov, Vladimir B.; Xie, Feng; Lyyra, A. Marjatta; Ahmed, Ergin H.; Ma, Jie; Jia, Suotang

2017-09-01

This paper clarifies the disagreement in the depth of the potential energy curve of the cesium dimer singlet ground state which has lasted for nearly a decade. We point out that the origin of this disagreement must be a technical misprint in the values of the three binding energies reported by Danzl et al. [Science 321, 1062 (2008)], while the X1Σg+ state potential reported by Coxon and Hajigeorgiou [J. Chem. Phys. 132, 094105 (2010)], based on experimental data by Amiot and Dulieu [J. Chem. Phys. 117, 5155 (2002)], is quite correct. We have recalculated the potential energy function of the triplet ground state a3Σu+ by using the available experimental data spanning both the attractive and the repulsive branches so that the potential energy function complies asymptotically with the singlet ground state X1Σg+ potential energy function by Coxon and Hajigeorgiou. This is important for the simulation of the near dissociation properties such as Feshbach resonances, which are typically observed in modern experiments with ultracold atoms and molecules.

Spin-Triplet Pairing Induced by Spin-Singlet Interactions in Noncentrosymmetric Superconductors

NASA Astrophysics Data System (ADS)

Matsuzaki, Tomoaki; Shimahara, Hiroshi

2017-02-01

In noncentrosymmetric superconductors, we examine the effect of the difference between the intraband and interband interactions, which becomes more important when the band splitting increases. We define the difference ΔVμ between their coupling constants, i.e., that between the intraband and interband hopping energies of intraband Cooper pairs. Here, the subscript μ of ΔVμ indicates that the interactions scatter the spin-singlet and spin-triplet pairs when μ = 0 and μ = 1,2,3, respectively. It is shown that the strong antisymmetric spin-orbit interaction reverses the target spin parity of the interaction: it converts the spin-singlet and spin-triplet interactions represented by ΔV0 and ΔVμ>0 into effective spin-triplet and spin-singlet pairing interactions, respectively. Hence, for example, triplet pairing can be induced solely by the singlet interaction ΔV0. We name the pairing symmetry of the system after that of the intraband Cooper pair wave function, but with an odd-parity phase factor excluded. The pairing symmetry must then be even, even for the triplet component, and the following results are obtained. When ΔVμ is small, the spin-triplet p-wave interactions induce spin-triplet s-wave and spin-triplet d-wave pairings in the regions where the repulsive singlet s-wave interaction is weak and strong, respectively. When ΔV0 is large, a repulsive interband spin-singlet interaction can stabilize spin-triplet pairing. When the Rashba interaction is adopted for the spin-orbit interaction, the spin-triplet pairing interactions mediated by transverse magnetic fluctuations do not contribute to triplet pairing.

Intracellular singlet oxygen photosensitizers: on the road to solving the problems of sensitizer degradation, bleaching and relocalization.

PubMed

da Silva, Elsa F F; Pimenta, Frederico M; Pedersen, Brian W; Blaikie, Frances H; Bosio, Gabriela N; Breitenbach, Thomas; Westberg, Michael; Bregnhøj, Mikkel; Etzerodt, Michael; Arnaut, Luis G; Ogilby, Peter R

2016-02-01

Selected singlet oxygen photosensitizers have been examined from the perspective of obtaining a molecule that is sufficiently stable under conditions currently employed to study singlet oxygen behavior in single mammalian cells. Reasonable predictions about intracellular sensitizer stability can be made based on solution phase experiments that approximate the intracellular environment (e.g., solutions containing proteins). Nevertheless, attempts to construct a stable sensitizer based solely on the expected reactivity of a given functional group with singlet oxygen are generally not sufficient for experiments in cells; it is difficult to construct a suitable chromophore that is impervious to all of the secondary and/or competing degradative processes that are present in the intracellular environment. On the other hand, prospects are reasonably positive when one considers the use of a sensitizer encapsulated in a specific protein; the local environment of the chromophore is controlled, degradation as a consequence of bimolecular reactions can be mitigated, and genetic engineering can be used to localize the encapsulated sensitizer in a given cellular domain. Also, the option of directly exciting oxygen in sensitizer-free experiments provides a useful complementary tool. These latter systems bode well with respect to obtaining more accurate control of the "dose" of singlet oxygen used to perturb a cell; a parameter that currently limits mechanistic studies of singlet-oxygen-mediated cell signaling.

Determination of Distance Distribution Functions by Singlet-Singlet Energy Transfer

PubMed Central

Cantor, Charles R.; Pechukas, Philip

1971-01-01

The efficiency of energy transfer between two chromophores can be used to define an apparent donor-acceptor distance, which in flexible systems will depend on the R0 of the chromophores. If efficiency is measured as a function of R0, it will be possible to determine the actual distribution function of donor-acceptor distances. Numerical procedures are described for extracting this information from experimental data. They should be most useful for distribution functions with mean values from 20-30 Å (2-3 nm). This technique should provide considerably more detailed information on end-to-end distributions of oligomers than has hitherto been available. It should also be useful for describing, in detail, conformational flexibility in other large molecules. PMID:16591942

Global potential energy surface of ground state singlet spin O4

NASA Astrophysics Data System (ADS)

Mankodi, Tapan K.; Bhandarkar, Upendra V.; Puranik, Bhalchandra P.

2018-02-01

A new global potential energy for the singlet spin state O4 system is reported using CASPT2/aug-cc-pVTZ ab initio calculations. The geometries for the six-dimensional surface are constructed using a novel point generation scheme that employs randomly generated configurations based on the beta distribution. The advantage of this scheme is apparent in the reduction of the number of required geometries for a reasonably accurate potential energy surface (PES) and the consequent decrease in the overall computational effort. The reported surface matches well with the recently published singlet surface by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. In addition to the O4 PES, the ground state N4 PES is also constructed using the point generation scheme and compared with the existing PES [Y. Paukku et al., J. Chem. Phys. 139, 044309 (2013)]. The singlet surface is constructed with the aim of studying high energy O2-O2 collisions and predicting collision induced dissociation cross section to be used in simulating non-equilibrium aerothermodynamic flows.

Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process

NASA Astrophysics Data System (ADS)

Feng, Jicheng; Biskos, George; Schmidt-Ott, Andreas

2015-10-01

Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure non-agglomerated “singlet” nanoparticles having tunable sizes at room temperature. By controlling the temperature in the particle growth zone to guarantee complete coalescence of colliding entities, the size of singlets in principle can be regulated from that of single atoms to any desired value. We assess our results in the context of a simple analytical model to explore the dependence of singlet size on the operating conditions. Agreement of the model with experimental measurements shows that these methods can be effectively used for producing singlets that can be processed further by many alternative approaches. Combined with the capabilities of up-scaling and unlimited mixing that spark ablation enables, this study provides an easy-to-use concept for producing the key building blocks for low-cost industrial-scale nanofabrication of advanced materials.

Electronic structure and normal vibrations of the 1-ethyl-3-methylimidazolium ethyl sulfate ion pair.

PubMed

Dhumal, Nilesh R; Kim, Hyung J; Kiefer, Johannes

2011-04-21

Electronic and structural properties of the ion pair 1-ethyl-3-methylimidazolium ethyl sulfate are studied using density functional methods. Three locally stable conformers of the ion pair complex are considered to analyze molecular interactions between its cation and anion. Manifestations of these interactions in the vibrational spectra are discussed and compared with experimental IR and Raman spectroscopy data. NBO analysis and difference electron density coupled with molecular electron density topography are used to interpret the frequency shifts of the normal vibrations of the ion pair, compared to the free anion and cation. Excitation energies of low-lying singlet excited states of the conformers are also studied. The density functional theory results are found to be in a reasonable agreement with experimental UV/vis absorption spectra.

Collective aspects of singlet fission in molecular crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teichen, Paul E.; Eaves, Joel D., E-mail: joel.eaves@colorado.edu

2015-07-28

We present a model to describe collective features of singlet fission in molecular crystals and analyze it using many-body theory. The model we develop allows excitonic states to delocalize over several chromophores which is consistent with the character of the excited states in many molecular crystals, such as the acenes, where singlet fission occurs. As singlet states become more delocalized and triplet states more localized, the rate of singlet fission increases. We also determine the conditions under which the two triplets resulting from fission are correlated. Using the Bethe Ansatz and an entanglement measure for indistinguishable bipartite systems, we calculatemore » the triplet-triplet entanglement as a function of the biexciton interaction strength. The biexciton interaction can produce bound biexciton states and provides a source of entanglement between the two triplets even when the triplets are spatially well separated. Significant entanglement between the triplet pair occurs well below the threshold for bound pair formation. Our results paint a dynamical picture that helps to explain why fission has been observed to be more efficient in molecular crystals than in their covalent dimer analogues and have consequences for photovoltaic efficiency models that assume that the two triplets can be extracted independently.« less

Theory and modeling of atmospheric turbulence, part 2

NASA Technical Reports Server (NTRS)

Chen, C. M.

1984-01-01

Two dimensional geostrophic turbulence driven by a random force is investigated. Based on the Liouville equation, which simulates the primitive hydrodynamical equations, a group-kinetic theory of turbulence is developed and the kinetic equation of the scaled singlet distribution is derived. The kinetic equation is transformed into an equation of spectral balance in the equilibrium and non-equilibrium states. Comparison is made between the propagators and the Green's functions in the case of the non-asymptotic quasi-linear equation to prove the equivalence of both kinds of approximations used to describe perturbed trajectories of plasma turbulence. The microdynamical state of fluid turbulence is described by a hydrodynamical system and transformed into a master equation analogous to the Vlasov equation for plasma turbulence. The spectral balance for the velocity fluctuations of individual components shows that the scaled pressure strain correlation and the cascade transfer are two transport functions that play the most important roles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango

Singlet fission, in which two triplet excitons are generated from a single absorbed photon, is a key third-generation solar cell concept. Conservation of angular momentum requires that singlet fission populates correlated multiexciton states, which can subsequently dissociate to generate free triplets. However, little is known about electronic and spin correlations in these systems since, due to its typically short lifetime, the multiexciton state is challenging to isolate and study. Here, we use bridged pentacene dimers, which undergo intramolecular singlet fission while isolated in solution and in solid matrices, as a unimolecular model system that can trap long-lived multiexciton states. Wemore » also combine transient absorption and time-resolved electron spin resonance spectroscopies to show that spin correlations in the multiexciton state persist for hundreds of nanoseconds. Furthermore, we confirm long-standing predictions that singlet fission produces triplet pair states of quintet character. Finally, we compare two different pentacene–bridge–pentacene chromophores, systematically tuning the coupling between the pentacenes to understand how differences in molecular structure affect the population and dissociation of multiexciton quintet states.« less

Explicit macroscopic singlet oxygen modeling for benzoporphyrin derivative monoacid ring A (BPD)-mediated photodynamic therapy.

PubMed

Kim, Michele M; Penjweini, Rozhin; Liang, Xing; Zhu, Timothy C

2016-11-01

Photodynamic therapy (PDT) is an effective non-ionizing treatment modality that is currently being used for various malignant and non-malignant diseases. In type II PDT with photosensitizers such as benzoporphyrin monoacid ring A (BPD), cell death is based on the creation of singlet oxygen ( 1 O 2 ). With a previously proposed empirical five-parameter macroscopic model, the threshold dose of singlet oxygen ([ 1 O 2 ] rx,sh ]) to cause tissue necrosis in tumors treated with PDT was determined along with a range of the magnitude of the relevant photochemical parameters: the photochemical oxygen consumption rate per light fluence rate and photosensitizer concentration (ξ), the probability ratio of 1 O 2 to react with ground state photosensitizer compared to a cellular target (σ), the ratio of the monomolecular decay rate of the triplet state photosensitizer (β), the low photosensitizer concentration correction factor (δ), and the macroscopic maximum oxygen supply rate (g). Mice bearing radiation-induced fibrosarcoma (RIF) tumors were treated interstitially with a linear light source at 690nm with total energy released per unit length of 22.5-135J/cm and source power per unit length of 12-150mW/cm to induce different radii of necrosis. A fitting algorithm was developed to determine the photochemical parameters by minimizing the error function involving the range between the calculated reacted singlet oxygen ([ 1 O 2 ] rx ) at necrosis radius and the [ 1 O 2 ] rx,sh . [ 1 O 2 ] rx was calculated based on explicit dosimetry of the light fluence distribution, the tissue optical properties, and the BPD concentration. The initial ground state oxygen concentration ([ 3 O 2 ] 0 ) was set to be 40μM in this study. The photochemical parameters were found to be ξ=(55±40)×10 -3 cm 2 mW -1 s -1 , σ=(1.8±3)×10 -5 μM -1 , and g=1.7±0.7μMs -1 . We have taken the literature values for δ=33μM, and β=11.9μM. [ 1 O 2 ] rx has shown promise to be a more effective dosimetry quantity for predicting necrosis than either light dose or PDT dose, where the latter is simplistically a temporal integral of the products of the photosensitizer concentration and light fluence rate. Copyright © 2016 Elsevier B.V. All rights reserved.

Structure of an electric double layer containing a 2:2 valency dimer electrolyte

DOE PAGES

Silvestre-Alcantara, Whasington; Henderson, Douglas; Wu, Jianzhong; ...

2014-12-05

In this study, the structure of a planar electric double layer formed by a 2:2 valency dimer electrolyte in the vicinity of a uniformly charged planar hard electrode is investigated using density functional theory and Monte Carlo simulations. The dimer electrolyte consists of a mixture of charged divalent dimers and charged divalent monomers in a dielectric continuum. A dimer is constructed by two tangentially tethered rigid spheres, one of which is divalent and positively charged and the other neutral, whereas the monomer is a divalent and negatively charged rigid sphere. The density functional theory reproduces well the simulation results formore » (i) the singlet distributions of the various ion species with respect to the electrode, and (ii) the mean electrostatic potential. Lastly, comparison with earlier results for a 2:1/1:2 dimer electrolyte shows that the double layer structure is similar when the counterion has the same valency.« less

Helicity Evolution at Small x

NASA Astrophysics Data System (ADS)

Sievert, Michael; Kovchegov, Yuri; Pitonyak, Daniel

2017-01-01

We construct small- x evolution equations which can be used to calculate quark and anti-quark helicity TMDs and PDFs, along with the g1 structure function. These evolution equations resum powers of ln2(1 / x) in the polarization-dependent evolution along with the powers of ln(1 / x) in the unpolarized evolution which includes saturation effects. The equations are written in an operator form in terms of polarization-dependent Wilson line-like operators. While the equations do not close in general, they become closed and self-contained systems of non-linear equations in the large-Nc and large-Nc &Nf limits. After solving the large-Nc equations numerically we obtain the following small- x asymptotics for the flavor-singlet g1 structure function along with quarks hPDFs and helicity TMDs (in absence of saturation effects): g1S(x ,Q2) ΔqS(x ,Q2) g1L S(x ,kT2) (1/x) > αh (1/x) 2.31√{αsNc/2 π. We also give an estimate of how much of the proton's spin may be at small x and what impact this has on the so-called ``spin crisis.'' Work supported by the U.S. DOE, Office of Science, Office of Nuclear Physics under Award Number DE-SC0004286 (YK), the RIKEN BNL Research Center, and TMD Collaboration (DP), and DOE Contract No. DE-SC0012704 (MS).

Anomalous enhancement of the lower critical field deep in the superconducting state of LaRu4As12

NASA Astrophysics Data System (ADS)

Juraszek, J.; Bochenek, Ł.; Wawryk, R.; Henkie, Z.; Konczykowski, M.; Cichorek, T.

2018-05-01

LaRu4As12 with the critical temperature Tc = 10.4 K displays several features which point at a non-singlet superconducting order parameter, although the bcc crystal structure of the filled skutterudites does not favour the emergence of multiple energy gaps. LaRu4As12 displays an unexpected enhancement of the lower critical field deep in superconducting state which can be attributed to the existence of two superconducting gaps. At T = 0.4 K, the local magnetization measurements were performed utilizing miniaturized Hall sensors.

Further Comments on a Vanishing Singlet Axial Vector Charge

NASA Astrophysics Data System (ADS)

Cheng, T. P.; Kochelev, N. I.; Vento, Vicente

The recent suggestion of a vanishing flavor-singlet axial-charge of nucleon due to a nontrivial vacuum structure is further amplified. A perturbative QCD discussion, applicable for the heavy quark contributions, relates it to the physics of the decoupling theorem. It is also shown that gA0˜= 0 leads to a negative η‧-meson-quark coupling, which has been found to be compatible with the chiral quark model phenomenology.

Distribution function of random strains in an elastically anisotropic continuum and defect strengths of T m3 + impurity ions in crystals with zircon structure

NASA Astrophysics Data System (ADS)

Malkin, B. Z.; Abishev, N. M.; Baibekov, E. I.; Pytalev, D. S.; Boldyrev, K. N.; Popova, M. N.; Bettinelli, M.

2017-07-01

We construct a distribution function of the strain-tensor components induced by point defects in an elastically anisotropic continuum, which can be used to account quantitatively for many effects observed in different branches of condensed matter physics. Parameters of the derived six-dimensional generalized Lorentz distribution are expressed through the integrals computed over the array of strains. The distribution functions for the cubic diamond and elpasolite crystals and tetragonal crystals with the zircon and scheelite structures are presented. Our theoretical approach is supported by a successful modeling of specific line shapes of singlet-doublet transitions of the T m3 + ions doped into AB O4 (A =Y , Lu; B =P , V) crystals with zircon structure, observed in high-resolution optical spectra. The values of the defect strengths of impurity T m3 + ions in the oxygen surroundings, obtained as a result of this modeling, can be used in future studies of random strains in different rare-earth oxides.

Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pederson, Mark R., E-mail: mark.pederson@science.doe.gov

2015-02-14

A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeitmore » slightly too low.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berkelbach, Timothy C., E-mail: tcb2112@columbia.edu; Reichman, David R., E-mail: drr2103@columbia.edu; Hybertsen, Mark S., E-mail: mhyberts@bnl.gov

We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singletmore » fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems.« less

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na3.13Mg1.43U6F30 and Na2.50Mn1.75U6F30: Structures, optical and magnetic properties

NASA Astrophysics Data System (ADS)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua; Möller, Angela; zur Loye, Hans-Conrad

2016-04-01

Two new uranium(IV) fluorides, Na3.13Mg1.43U6F30 (1) and Na2.50Mn1.75U6F30 (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF9 and MF6 (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F6 octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site. Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 μB for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV-vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed.

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

PubMed Central

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

Non-Born-Oppenheimer molecular dynamics of the spin-forbidden reaction O(3P) + CO(X 1Σ+) → CO2(tilde X{}^1Σ _g^ +)

NASA Astrophysics Data System (ADS)

Jasper, Ahren W.; Dawes, Richard

2013-10-01

The lowest-energy singlet (1 1A') and two lowest-energy triplet (1 3A' and 1 3A″) electronic states of CO2 are characterized using dynamically weighted multireference configuration interaction (dw-MRCI+Q) electronic structure theory calculations extrapolated to the complete basis set (CBS) limit. Global analytic representations of the dw-MRCI+Q/CBS singlet and triplet surfaces and of their CASSCF/aug-cc-pVQZ spin-orbit coupling surfaces are obtained via the interpolated moving least squares (IMLS) semiautomated surface fitting method. The spin-forbidden kinetics of the title reaction is calculated using the coupled IMLS surfaces and coherent switches with decay of mixing non-Born-Oppenheimer molecular dynamics. The calculated spin-forbidden association rate coefficient (corresponding to the high pressure limit of the rate coefficient) is 7-35 times larger at 1000-5000 K than the rate coefficient used in many detailed chemical models of combustion. A dynamical analysis of the multistate trajectories is presented. The trajectory calculations reveal direct (nonstatistical) and indirect (statistical) spin-forbidden reaction mechanisms and may be used to test the suitability of transition-state-theory-like statistical methods for spin-forbidden kinetics. Specifically, we consider the appropriateness of the "double passage" approximation, of assuming statistical distributions of seam crossings, and of applications of the unified statistical model for spin-forbidden reactions.

Towards a global model of spin-orbit coupling in the halocarbenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nyambo, Silver; Karshenas, Cyrus; Reid, Scott A., E-mail: scott.reid@marquette.edu, E-mail: dawesr@mst.edu

We report a global analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, and I. These are model systems for examining carbene singlet-triplet energy gaps and spin-orbit coupling. Over the past decade, rich data sets collected using single vibronic level emission spectroscopy and stimulated emission pumping spectroscopy have yielded much information on the ground vibrational level structure and clearly demonstrated the presence of perturbations involving the low-lying triplet state. To model these interactions globally, we compare two approaches. First, we employ a diabatic treatment of the spin-orbit coupling, where the coupling matrix elements are written inmore » terms of a purely electronic spin-orbit matrix element which is independent of nuclear coordinates, and an integral representing the overlap of the singlet and triplet vibrational wavefunctions. In this way, the structures, harmonic frequencies, and normal mode displacements from ab initio calculations were used to calculate the vibrational overlaps of the singlet and triplet state levels, including the full effects of Duschinsky mixing. These calculations have allowed many new assignments to be made, particularly for CHI, and provided spin-orbit coupling parameters and values for the singlet-triplet gaps. In a second approach, we have computed and fit full geometry dependent spin-orbit coupling surfaces and used them to compute matrix elements without the product form approximation. Those matrix elements were used in similar fits varying the anharmonic constants and singlet-triplet gap to reproduce the experimental levels. The derived spin-orbit parameters for carbenes CHX (X = Cl, Br, and I) show an excellent linear correlation with the atomic spin-orbit constant of the corresponding halogen, indicating that the spin-orbit coupling in the carbenes is consistently around 14% of the atomic value.« less

Development of Singlet Oxygen Luminescence Kinetics during the Photodynamic Inactivation of Green Algae.

PubMed

Bornhütter, Tobias; Pohl, Judith; Fischer, Christian; Saltsman, Irena; Mahammed, Atif; Gross, Zeev; Röder, Beate

2016-04-13

Recent studies show the feasibility of photodynamic inactivation of green algae as a vital step towards an effective photodynamic suppression of biofilms by using functionalized surfaces. The investigation of the intrinsic mechanisms of photodynamic inactivation in green algae represents the next step in order to determine optimization parameters. The observation of singlet oxygen luminescence kinetics proved to be a very effective approach towards understanding mechanisms on a cellular level. In this study, the first two-dimensional measurement of singlet oxygen kinetics in phototrophic microorganisms on surfaces during photodynamic inactivation is presented. We established a system of reproducible algae samples on surfaces, incubated with two different cationic, antimicrobial potent photosensitizers. Fluorescence microscopy images indicate that one photosensitizer localizes inside the green algae while the other accumulates along the outer algae cell wall. A newly developed setup allows for the measurement of singlet oxygen luminescence on the green algae sample surfaces over several days. The kinetics of the singlet oxygen luminescence of both photosensitizers show different developments and a distinct change over time, corresponding with the differences in their localization as well as their photosensitization potential. While the complexity of the signal reveals a challenge for the future, this study incontrovertibly marks a crucial, inevitable step in the investigation of photodynamic inactivation of biofilms: it shows the feasibility of using the singlet oxygen luminescence kinetics to investigate photodynamic effects on surfaces and thus opens a field for numerous investigations.

Probing the intrinsic electronic structure of the bis(dithiolene) anions [M(mnt)2]2- and [M(mnt)2]1- (M = Ni, Pd, Pt; mnt = 1,2-S2C2(CN)2) in the gas phase by photoelectron spectroscopy.

PubMed

Waters, Tom; Woo, Hin-Koon; Wang, Xue-Bin; Wang, Lai-Sheng

2006-04-05

A detailed understanding of the electronic structure of transition metal bis(dithiolene) complexes is important because of their interesting redox, magnetic, optical, and conducting properties and their relevance to enzymes containing molybdenum and tungsten bis(dithiolene) centers. The electronic structures of the bis(dithiolene) anions [M(mnt)(2)](n-) (M = Ni, Pd, Pt; mnt = 1,2-S(2)C(2)(CN)(2); n = 0-2) were examined by a combination of photodetachment photoelectron spectroscopy (PES) and density functional theory calculations. The combined experimental and theoretical data provide insight into the molecular orbital energy levels of [M(mnt)(2)](2-) and the ground and excited states of [M(mnt)(2)](1-) and [M(mnt)(2)]. Detachment features from ligand-based orbitals of [M(mnt)(2)](2-) occur at similar energies for each species, independent of the metal center, while those arising from metal-based orbitals occur at higher energies for the heavier congeners. Electronic excitation energies inferred for [M(mnt)(2)](1-) from the PES experiments agree well with those obtained in optical absorption experiments in solution, with the PES experiments providing additional insight into the changes in energy of these transitions as a function of metal. The singly charged anions [M(mnt)(2)](1-) were also prepared and studied independently. Electron detachment from the ground states of these doublet anions accessed the lowest singlet and triplet states of neutral [M(mnt)(2)], thereby providing a direct experimental measure of their singlet-triplet splitting.

Predicting apparent singlet oxygen quantum yields of dissolved black carbon and humic substances using spectroscopic indices.

PubMed

Du, Ziyan; He, Yingsheng; Fan, Jianing; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Qu, Xiaolei; Kong, Ao; Zhu, Dongqiang

2018-03-01

Dissolved black carbon (DBC) is ubiquitous in aquatic systems, being an important subgroup of the dissolved organic matter (DOM) pool. Nevertheless, its aquatic photoactivity remains largely unknown. In this study, a range of spectroscopic indices of DBC and humic substance (HS) samples were determined using UV-Vis spectroscopy, fluorescence spectroscopy, and proton nuclear magnetic resonance. DBC can be readily differentiated from HS using spectroscopic indices. It has lower average molecular weight, but higher aromaticity and lignin content. The apparent singlet oxygen quantum yield (Φ singlet oxygen ) of DBC under simulated sunlight varies from 3.46% to 6.13%, significantly higher than HS, 1.26%-3.57%, suggesting that DBC is the more photoactive component in the DOM pool. Despite drastically different formation processes and structural properties, the Φ singlet oxygen of DBC and HS can be well predicted by the same simple linear regression models using optical indices including spectral slope coefficient (S 275-295 ) and absorbance ratio (E 2 /E 3 ) which are proxies for the abundance of singlet oxygen sensitizers and for the significance of intramolecular charge transfer interactions. The regression models can be potentially used to assess the photoactivity of DOM at large scales with in situ water spectrophotometry or satellite remote sensing. Copyright © 2017 Elsevier Ltd. All rights reserved.

Generation of singlet oxygen in fullerene-containing media: 2. Fullerene-containing solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bagrov, I V; Belousova, I M; Grenishin, A S

2008-03-31

The generation of singlet oxygen in fullerene solutions is studied by luminescence methods upon excitation by pulsed, repetitively pulsed, and continuous radiation sources. The concentration of singlet oxygen in solutions is measured in stationary and pulsed irradiation regimes. The rate constants of quenching of O{sub 2}({sup 1}{delta}{sub g}) by fullerenes C{sub 70} and C{sub 60} in the CCl{sub 4} solution are measured to be (7.2{+-}0.1)x10{sup 7} L mol{sup -1} s{sup -1} and less than 6x10{sup 4} L mol{sup -1} s{sup -1}, respectively. The temperature and photolytic variations in the generation properties of the fullerene solution exposed to intense continuous radiationmore » are studied by the methods of optical and EPR spectroscopy. Pulsed irradiation resulted in the production of singlet oxygen in suspensions of fullerene-like structures, in particular, astralenes. A liquid pulsed singlet-oxygen generator based on the fullerene solution in CCl{sub 4} is developed and studied, in which the yield of O{sub 2} ({sup 1}{delta}{sub g}) to the gas phase at concentrations up to 5x10{sup 16} cm{sup -3} is obtained. (laser applications and other topics in quantum electronics)« less

A Possible Role for Singlet Oxygen in the Degradation of Various Antioxidants. A Meta-Analysis and Review of Literature Data

PubMed Central

Petrou, Athinoula L.; Petrou, Petros L.; Ntanos, Theodoros; Liapis, Antonis

2018-01-01

The thermodynamic parameters Eact, ΔH≠, ΔS≠, and ΔG≠ for various processes involving antioxidants were calculated using literature kinetic data (k, T). The ΔG≠ values of the antioxidants’ processes vary in the range 91.27–116.46 kJmol−1 at 310 K. The similarity of the ΔG≠ values (for all of the antioxidants studied) is supported to be an indication that a common mechanism in the above antioxidant processes may be taking place. A value of about 10–30 kJmol−1 is the activation energy for the diffusion of reactants depending on the reaction and the medium. The energy 92 kJmol−1 is needed for the excitation of O2 from the ground to the first excited state (1Δg, singlet oxygen). We suggest the same role of the oxidative stress and specifically of singlet oxygen to the processes of antioxidants as in the processes of proteinaceous diseases. We therefore suggest a competition between the various antioxidants and the proteins of proteinaceous diseases in capturing singlet oxygen’s empty π* orbital. The concentration of the antioxidants could be a crucial factor for the competition. Also, the structures of the antioxidant molecules play a significant role since the various structures have a different number of regions of high electron density. PMID:29495515

Calculated momentum dependence of Zhang-Rice states in transition metal oxides.

PubMed

Yin, Quan; Gordienko, Alexey; Wan, Xiangang; Savrasov, Sergey Y

2008-02-15

Using a combination of local density functional theory and cluster exact diagonalization based dynamical mean field theory, we calculate many-body electronic structures of several Mott insulating oxides including undoped high T(c) materials. The dispersions of the lowest occupied electronic states are associated with the Zhang-Rice singlets in cuprates and with doublets, triplets, quadruplets, and quintets in more general cases. Our results agree with angle resolved photoemission experiments including the decrease of the spectral weight of the Zhang-Rice band as it approaches k=0.

Nitroxide free radicals protect macular carotenoids against chemical destruction (bleaching) during lipid peroxidation

PubMed Central

Zareba, M.; Widomska, J.; Burke, J. M.; Subczynski, W. K.

2016-01-01

Macular xanthophylls (MXs) lutein and zeaxanthin are dietary carotenoids that are selectively concentrated in the human eye retina, where they are thought to protect against age-related macular degeneration (AMD) by multiple mechanisms, including filtration of phototoxic blue light and quenching of singlet oxygen and triplet states of photosensitizers. These physical protective mechanisms require that MXs be in their intact structure. Here, we investigated the protection of the intact structure of zeaxanthin incorporated into model membranes subjected to oxidative modification by water- and/or membrane-soluble small nitroxide free radicals. Model membranes were formed from saturated, monounsaturated, and polyunsaturated phosphatidylcholines (PCs). Oxidative modification involved autoxidation, iron-mediated, and singlet oxygen-mediated lipid peroxidation. The extent of chemical destruction (bleaching) of zeaxanthin was evaluated from its absorption spectra and compared with the extent of lipid peroxidation evaluated using the thiobarbituric acid assay. Nitroxide free radicals with different polarity (membrane/water partition coefficients) were used. The extent of zeaxanthin bleaching increased with membrane unsaturation and correlated with the rate of PC oxidation. Protection of the intact structure of zeaxanthin by membrane-soluble nitroxides was much stronger than that by water-soluble nitroxides. The combination of zeaxanthin and lipid-soluble nitroxides exerted strong synergistic protection against singlet oxygen-induced lipid peroxidation. The synergistic effect may be explained in terms of protection of the intact zeaxanthin structure by effective scavenging of free radicals by nitroxides, therefore allowing zeaxanthin to quench the primary oxidant, singlet oxygen, effectively by the physical protective mechanism. The redox state of nitroxides was monitored using electron paramagnetic resonance spectroscopy. Both nitroxide free radicals and their reduced form, hydroxylamines, were equally effective. Obtained data were compared with the protective effects of α-tocopherol, which is the natural antioxidant and protector of MXs within the retina. The new strategies employed here to maintain the intact structure of MXs may enhance their protective potential against AMD. PMID:27840316

Nitroxide free radicals protect macular carotenoids against chemical destruction (bleaching) during lipid peroxidation.

PubMed

Zareba, M; Widomska, J; Burke, J M; Subczynski, W K

2016-12-01

Macular xanthophylls (MXs) lutein and zeaxanthin are dietary carotenoids that are selectively concentrated in the human eye retina, where they are thought to protect against age-related macular degeneration (AMD) by multiple mechanisms, including filtration of phototoxic blue light and quenching of singlet oxygen and triplet states of photosensitizers. These physical protective mechanisms require that MXs be in their intact structure. Here, we investigated the protection of the intact structure of zeaxanthin incorporated into model membranes subjected to oxidative modification by water- and/or membrane-soluble small nitroxide free radicals. Model membranes were formed from saturated, monounsaturated, and polyunsaturated phosphatidylcholines (PCs). Oxidative modification involved autoxidation, iron-mediated, and singlet oxygen-mediated lipid peroxidation. The extent of chemical destruction (bleaching) of zeaxanthin was evaluated from its absorption spectra and compared with the extent of lipid peroxidation evaluated using the thiobarbituric acid assay. Nitroxide free radicals with different polarity (membrane/water partition coefficients) were used. The extent of zeaxanthin bleaching increased with membrane unsaturation and correlated with the rate of PC oxidation. Protection of the intact structure of zeaxanthin by membrane-soluble nitroxides was much stronger than that by water-soluble nitroxides. The combination of zeaxanthin and lipid-soluble nitroxides exerted strong synergistic protection against singlet oxygen-induced lipid peroxidation. The synergistic effect may be explained in terms of protection of the intact zeaxanthin structure by effective scavenging of free radicals by nitroxides, therefore allowing zeaxanthin to quench the primary oxidant, singlet oxygen, effectively by the physical protective mechanism. The redox state of nitroxides was monitored using electron paramagnetic resonance spectroscopy. Both nitroxide free radicals and their reduced form, hydroxylamines, were equally effective. Obtained data were compared with the protective effects of α-tocopherol, which is the natural antioxidant and protector of MXs within the retina. The new strategies employed here to maintain the intact structure of MXs may enhance their protective potential against AMD. Copyright © 2016 Elsevier Inc. All rights reserved.

Beyond Born-Oppenheimer theory for ab initio constructed diabatic potential energy surfaces of singlet H3+ to study reaction dynamics using coupled 3D time-dependent wave-packet approach.

PubMed

Ghosh, Sandip; Mukherjee, Saikat; Mukherjee, Bijit; Mandal, Souvik; Sharma, Rahul; Chaudhury, Pinaki; Adhikari, Satrajit

2017-08-21

The workability of beyond Born-Oppenheimer theory to construct diabatic potential energy surfaces (PESs) of a charge transfer atom-diatom collision process has been explored by performing scattering calculations to extract accurate integral cross sections (ICSs) and rate constants for comparison with most recent experimental quantities. We calculate non-adiabatic coupling terms among the lowest three singlet states of H 3 + system (1 1 A ' , 2 1 A ' , and 3 1 A ' ) using MRCI level of calculation and solve the adiabatic-diabatic transformation equation to formulate the diabatic Hamiltonian matrix of the same process [S. Mukherjee et al., J. Chem. Phys. 141, 204306 (2014)] for the entire region of nuclear configuration space. The nonadiabatic effects in the D + + H 2 reaction has been studied by implementing the coupled 3D time-dependent wave packet formalism in hyperspherical coordinates [S. Adhikari and A. J. C. Varandas, Comput. Phys. Commun. 184, 270 (2013)] with zero and non-zero total angular momentum (J) on such newly constructed accurate (ab initio) diabatic PESs of H 3 + . We have depicted the convergence profiles of reaction probabilities for the reactive non-charge transfer, non-reactive charge transfer, and reactive charge transfer processes for different collisional energies with respect to the helicity (K) and total angular momentum (J) quantum numbers. Finally, total and state-to-state ICSs are calculated as a function of collision energy for the initial rovibrational state (v = 0, j = 0) of the H 2 molecule, and consequently, those quantities are compared with previous theoretical and experimental results.

Intramolecular charge transfer and trans-cis isomerization of the DCM styrene dye in polar solvents. A CS INDO MRCI study

NASA Astrophysics Data System (ADS)

Marguet, S.; Mialocq, J. C.; Millie, P.; Berthier, G.; Momicchioli, F.

1992-03-01

The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central "double" bond and the twisting of the dimethylamino group, have been obtained for the ground state and the lowest excited states. The structural requirements for the existence of ICT (intramolecular charge transfer) excited states have been investigated by considering internal rotations about three single bonds. The reliability of the potential surfaces and of the solvation models has been discussed with reference to test-calculations on the DMABN molecule. In the first excited singlet state of DCM, the low-energy barrier for the trans-cis isomerization has been found unaffected by the solvent polarity. The only singlet excited state presenting a large ICT character has been found to be the S 2 state for a perpendicularly twisted conformation of the dimethylamino group (TICT state). The assumption of a deactivation of the trans-isomer in the locally excited state through the TICT funnel has been largely discussed with reference to the simplifications of the present theoretical approach.

Twisted cyanines: a non-planar fluorogenic dye with superior photostability and its use in a protein-based fluoromodule.

PubMed

Shank, Nathaniel I; Pham, Ha H; Waggoner, Alan S; Armitage, Bruce A

2013-01-09

The cyanine dye thiazole orange (TO) is a well-known fluorogenic stain for DNA and RNA, but this property precludes its use as an intracellular fluorescent probe for non-nucleic acid biomolecules. Further, as is the case with many cyanines, the dye suffers from low photostability. Here, we report the synthesis of a bridge-substituted version of TO named α-CN-TO, where the central methine hydrogen of TO is replaced by an electron withdrawing cyano group, which was expected to decrease the susceptibility of the dye toward singlet oxygen-mediated degradation. An X-ray crystal structure shows that α-CN-TO is twisted drastically out of plane, in contrast to TO, which crystallizes in the planar conformation. α-CN-TO retains the fluorogenic behavior of the parent dye TO in viscous glycerol/water solvent, but direct irradiation and indirect bleaching studies showed that α-CN-TO is essentially inert to visible light and singlet oxygen. In addition, the twisted conformation of α-CN-TO mitigates nonspecific binding and fluorescence activation by DNA and a previously selected TO-binding protein and exhibits low background fluorescence in HeLa cell culture. α-CN-TO was then used to select a new protein that binds and activates fluorescence from the dye. The new α-CN-TO/protein fluoromodule exhibits superior photostability to an analogous TO/protein fluoromodule. These properties indicate that α-CN-TO will be a useful fluorogenic dye in combination with specific RNA and protein binding partners for both in vitro and cell-based applications. More broadly, structural features that promote nonplanar conformations can provide an effective method for reducing nonspecific binding of cationic dyes to nucleic acids and other biomolecules.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, II, Barry; Schrader, Robert L.; Kowalski, Karol

The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals ledmore » to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.« less

Molecular-Barrier-Enhanced Aromatic Fluorophores in Cocrystals with Unity Quantum Efficiency.

PubMed

Ye, Huanqing; Liu, Guangfeng; Liu, Sheng; Casanova, David; Ye, Xin; Tao, Xutang; Zhang, Qichun; Xiong, Qihua

2018-02-12

Singlet-triplet conversion in organic light-emitting materials introduces non-emissive (dark) and long-lived triplet states, which represents a significant challenge in constraining the optical properties. There have been considerable attempts at separating singlets and triplets in long-chain polymers, scavenging triplets, and quenching triplets with heavy metals; nonetheless, such triplet-induced loss cannot be fully eliminated. Herein, a new strategy of crafting a periodic molecular barrier into the π-conjugated matrices of organic aromatic fluorophores is reported. The molecular barriers effectively block the singlet-to-triplet pathway, resulting in near-unity photoluminescence quantum efficiency (PLQE) of the organic fluorophores. The transient optical spectroscopy measurements confirm the absence of the triplet absorption. These studies provide a general approach to preventing the formation of dark triplet states in organic semiconductors and bring new opportunities for the development of advanced organic optics and photonics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of H2 binding on the nonadiabatic transition probability between singlet and triplet states of the [NiFe]-hydrogenase active site.

PubMed

Kaliakin, Danil S; Zaari, Ryan R; Varganov, Sergey A

2015-02-12

We investigate the effect of H2 binding on the spin-forbidden nonadiabatic transition probability between the lowest energy singlet and triplet electronic states of [NiFe]-hydrogenase active site model, using a velocity averaged Landau-Zener theory. Density functional and multireference perturbation theories were used to provide parameters for the Landau-Zener calculations. It was found that variation of the torsion angle between the terminal thiolate ligands around the Ni center induces an intersystem crossing between the lowest energy singlet and triplet electronic states in the bare active site and in the active site with bound H2. Potential energy curves between the singlet and triplet minima along the torsion angle and H2 binding energies to the two spin states were calculated. Upon H2 binding to the active site, there is a decrease in the torsion angle at the minimum energy crossing point between the singlet and triplet states. The probability of nonadiabatic transitions at temperatures between 270 and 370 K ranges from 35% to 32% for the active site with bound H2 and from 42% to 38% for the bare active site, thus indicating the importance of spin-forbidden nonadiabatic pathways for H2 binding on the [NiFe]-hydrogenase active site.

Temporal profile of the singlet oxygen emission endogenously produced by photosystem II reaction centre in an aqueous buffer.

PubMed

Li, Heng; Melø, Thor Bernt; Arellano, Juan B; Razi Naqvi, K

2012-04-01

The temporal profile of the phosphorescence of singlet oxygen endogenously photosensitized by photosystem II (PSII) reaction centre (RC) in an aqueous buffer has been recorded using laser excitation and a near infrared photomultiplier tube. A weak emission signal was discernible, and could be fitted to the functional form a[exp(-t/τ(2) - exp(-t/τ(1)], with a > 0 and τ(2) > τ(1). The value of τ(2) decreased from 11.6 ± 0.5 μs under aerobic conditions to 4.1 ± 0.2 μs in oxygen-saturated samples, due to enhanced bimolecular quenching of the donor triplet by oxygen, whereas that of τ(1), identifiable with the lifetime of singlet oxygen, was close to 3 μs in both cases. Extrapolations based on the low amplitude of the emission signal of singlet oxygen formed by PSII RC in the aqueous buffer and the expected values of τ(1) and τ(2) in chloroplasts indicate that attempts to analyse the temporal profile of singlet oxygen in chloroplasts are unlikely to be rewarded with success without a significant advance in the sensitivity of the detection equipment. © Springer Science+Business Media B.V. 2012

Effect of intramolecular charge transfer on fluorescence and singlet oxygen production of phthalocyanine analogues.

PubMed

Vachova, Lenka; Novakova, Veronika; Kopecky, Kamil; Miletin, Miroslav; Zimcik, Petr

2012-10-14

Intramolecular charge transfer (ICT) was studied on a series of magnesium, metal-free and zinc complexes of unsymmetrical tetrapyrazinoporphyrazines and tribenzopyrazinoporphyrazines bearing two dialkylamino substituents (donors) and six alkylsulfanyl or aryloxy substituents (non-donors). The dialkylamino substituents were responsible for ICT that deactivated excited states and led to considerable decrease of fluorescence and singlet oxygen quantum yields. Photophysical and photochemical properties were compared to corresponding macrocycles that do not bear any donor centers. The data showed high feasibility of ICT in the tetrapyrazinoporphyrazine macrocycle and significantly lower efficiency of this deactivation process in the tribenzopyrazinoporphyrazine type molecules. Considerable effect of non-donor peripheral substituents on ICT was also described. The results imply that tetrapyrazinoporphyrazines may be more suitable for development of new molecules investigated in applications based on ICT.

Singlet Oxygen Generation Mediated By Silicon Nanocrystal Assemblies

DTIC Science & Technology

2011-01-01

Lattice fringes in Fig.3 d correspond to the (111) atomic planes of Si nanocrystals. Length scales are indicated. Downscaling of the stain etched PSi...intensity of 1W/cm2 in a time scale of a few hours a monolayer of oxygen is formed on the surface of Si nanocrystals. Fig. 8. Infrared absorption...solution. Fig. 10. PL intensity as a function of continuously prolonged etching of Si powder. Inset: PL suppression level (can be scaled as singlet

Structural and magnetic properties of the 5d 2 double perovskites Sr 2 BReO 6 ( B = Y, In)

DOE PAGES

Aczel, A. A.; Zhao, Z.; Calder, S.; ...

2016-06-01

With this study, we have performed magnetic susceptibility, heat capacity, neutron powder diffraction, and muon spin relaxation experiments to investigate the magnetic ground states of the 5more » $d^2$ double perovskites Sr$$_2$$YReO$$_6$$ and Sr$$_2$$InReO$$_6$$. We find that Sr$$_2$$YReO$$_6$$ is a spin glass, while Sr$$_2$$InReO$$_6$$ hosts a non-magnetic singlet state. By making detailed comparisons with other 5$d^2$ double perovskites, we argue that a delicate interplay between spin-orbit coupling, non-cubic crystal fields, and exchange interactions plays a key role in the great variation of magnetic ground states observed for this family of materials.« less

Double Parton Fragmentation Function and its Evolution in Quarkonium Production

NASA Astrophysics Data System (ADS)

Kang, Zhong-Bo

2014-01-01

We summarize the results of a recent study on a new perturbative QCD factorization formalism for the production of heavy quarkonia of large transverse momentum pT at collider energies. Such a new factorization formalism includes both the leading power (LP) and next-to-leading power (NLP) contributions to the cross section in the mQ2/p_T^2 expansion for heavy quark mass mQ. For the NLP contribution, the so-called double parton fragmentation functions are involved, whose evolution equations have been derived. We estimate fragmentation functions in the non-relativistic QCD formalism, and found that their contribution reproduce the bulk of the large enhancement found in explicit NLO calculations in the color singlet model. Heavy quarkonia produced from NLP channels prefer longitudinal polarization, in contrast to the single parton fragmentation function. This might shed some light on the heavy quarkonium polarization puzzle.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

NASA Astrophysics Data System (ADS)

Zhang, Xian-Fu; Feng, Nan

2018-01-01

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 < δ ≤ 1), and the charge recombination induced the formation of triplet state (Dδ +-Aδ - → D-A (T1). These novel PCT- or PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

Flavonoids in Microheterogeneous Media, Relationship between Their Relative Location and Their Reactivity towards Singlet Oxygen

PubMed Central

Günther, Germán; Berríos, Eduardo; Pizarro, Nancy; Valdés, Karina; Montero, Guillermo; Arriagada, Francisco; Morales, Javier

2015-01-01

In this work, the relationship between the molecular structure of three flavonoids (kaempferol, quercetin and morin), their relative location in microheterogeneous media (liposomes and erythrocyte membranes) and their reactivity against singlet oxygen was studied. The changes observed in membrane fluidity induced by the presence of these flavonoids and the influence of their lipophilicity/hydrophilicity on the antioxidant activity in lipid membranes were evaluated by means of fluorescent probes such as Laurdan and diphenylhexatriene (DPH). The small differences observed for the value of generalized polarization of Laurdan (GP) curves in function of the concentration of flavonoids, indicate that these three compounds promote similar alterations in liposomes and erythrocyte membranes. In addition, these compounds do not produce changes in fluorescence anisotropy of DPH, discarding their location in deeper regions of the lipid bilayer. The determined chemical reactivity sequence is similar in all the studied media (kaempferol < quercetin < morin). Morin is approximately 10 times more reactive than quercetin and 20 to 30 times greater than kaempferol, depending on the medium. PMID:26098745

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

PubMed

Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

2016-02-01

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

Singlet-triplet splittings and their relevance to the spin-dependent exciton formation in light-emitting polymers: an EOM/CCSD study.

PubMed

Chen, Liping; Zhu, Lingyun; Shuai, Zhigang

2006-12-21

By employing the coupled-cluster equation of motion method (EOM/CCSD) for excited-state structures, we have investigated the structure dependence of the singlet and triplet exciton splittings, through extensive calculations for polythiophene (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(thienylenevinylene) (PTV), polyparaphenylene vinylene (PPV), MEHPPV, polyparaphenylene ethylene (PPE), polyfluorene (PFO), and ladder-type polyparaphenylene (mLPPP). The results for the polymer are extrapolated through computations for the oligomers with increasing length. Recent investigations have been quite controversial about whether the internal quantum efficiency of electroluminescence could be higher than the 25% spin statistics limit or not in polymeric materials. Using a simple relationship between the exciton formation rate and the excitation energy level, we have discussed the material-dependent ratios of singlet and triplet exciton formation, which are in good agreement with the magnetic-field resonance detected transient spectroscopy measurement by Wohlgenannt et al. for a series of electronic polymers. This provides another piece of evidence to support the view that the internal quantum efficiency for conjugated polymers can exceed the 25% limit.

Triazatruxene: A Rigid Central Donor Unit for a D-A3 Thermally Activated Delayed Fluorescence Material Exhibiting Sub-Microsecond Reverse Intersystem Crossing and Unity Quantum Yield via Multiple Singlet-Triplet State Pairs.

PubMed

Dos Santos, Paloma L; Ward, Jonathan S; Congrave, Daniel G; Batsanov, Andrei S; Eng, Julien; Stacey, Jessica E; Penfold, Thomas J; Monkman, Andrew P; Bryce, Martin R

2018-06-01

By inverting the common structural motif of thermally activated delayed fluorescence materials to a rigid donor core and multiple peripheral acceptors, reverse intersystem crossing (rISC) rates are demonstrated in an organic material that enables utilization of triplet excited states at faster rates than Ir-based phosphorescent materials. A combination of the inverted structure and multiple donor-acceptor interactions yields up to 30 vibronically coupled singlet and triplet states within 0.2 eV that are involved in rISC. This gives a significant enhancement to the rISC rate, leading to delayed fluorescence decay times as low as 103.9 ns. This new material also has an emission quantum yield ≈1 and a very small singlet-triplet gap. This work shows that it is possible to achieve both high photoluminescence quantum yield and fast rISC in the same molecule. Green organic light-emitting diode devices with external quantum efficiency >30% are demonstrated at 76 cd m -2 .

Heat of formation determination of the ground and excited state of cyanomethylene (HCCN) radical

NASA Technical Reports Server (NTRS)

Francisco, Joseph S.

1994-01-01

Ab initio electronic structure theory has been used to characterize the structure of the ground triplet and lowest singlet excited states of cyanomethylene. The geometries, vibrational frequencies, and heats of formation have been determined using second-order Moller-Plesset perturbation, single and double excitation configuration interaction, and quadratic configuration interaction theory. The heat of formation is predicted with isodesmic reaction and Gaussian-2 theory (G2) for the ground triplet and first excited singlet states of cyanomethylene. For the ground state Delta-H(sub 0)(sup f,0) is 114.8+/-2 kcal/mol while for the excited single state it is 126.5+/-2 kcal/mol.

The spectroscopy of singlets and triplets excites electronic states, spatial and electronic structure of hydrocarbons and quantum classifications in chemmotology

NASA Astrophysics Data System (ADS)

Obukhov, A. E.

2017-01-01

In this work we demonstrate the physical foundations of the spectroscopy of the grounds states: E- and X-ray, (RR) Raman scattering the NMR 1H and 13C and IR-, EPR- absorption and the singlets and triplets electronic excited states in the multinuclear hydrocarbons in chemmotology. The parameters of UV-absorption, RR-Raman scattering of light, the fluorescence and the phosphorescence and day-lasers at the pumping laser and lamp, OLEDs and OTETs- are measurements. The spectral-energy properties are briefly studied. The quantum-chemical LCAO-MO SCF expanded-CI PPP/S and INDO/S methods in the electronic and spatial structure hidrocarbons are considered.

Redox signaling and stress tolerance in plants: a focus on vitamin E.

PubMed

Miret, Javier A; Munné-Bosch, Sergi

2015-03-01

Plants are subject to specific redox processes, in which photosynthesis plays a prominent role. Chloroplasts function in light at high oxygen tensions and are enormous generators of reactive oxygen species, mainly singlet oxygen. This side product of photosynthesis inflicts damage to thylakoid membranes at high concentrations, but at the same time it is an essential component of cellular signaling. Detoxification of singlet oxygen is achieved by different means, including quenching and scavenging by tocopherols, responsible for controlling singlet oxygen levels, and the extent of lipid peroxidation in chloroplasts. Here, environmental conditions leading to excess light in chloroplasts will be used to show the importance of singlet oxygen, tocopherols, and lipid peroxidation in cell signaling. Defects in antioxidant protection (e.g., tocopherol deficiency) can lead to increased photo-oxidative damage, but also to the activation of defense pathways, illustrating the phenotypic plasticity evolved by plants to withstand stress. Most importantly, these studies show how redox signaling processes are integrated within the cell and illustrate the great capacity of plants to adapt to their environment. © 2015 New York Academy of Sciences.

A Classic Near-Infrared Probe Indocyanine Green for Detecting Singlet Oxygen.

PubMed

Tang, Cheng-Yi; Wu, Feng-Yao; Yang, Min-Kai; Guo, Yu-Min; Lu, Gui-Hua; Yang, Yong-Hua

2016-02-06

The revelation of mechanisms of photodynamic therapy (PDT) at the cellular level as well as singlet oxygen (¹O₂) as a second messengers requires the quantification of intracellular ¹O₂. To detect singlet oxygen, directly measuring the phosphorescence emitted from ¹O₂ at 1270 nm is simple but limited for the low quantum yield and intrinsic efficiency of ¹O₂ emission. Another method is chemically trapping ¹O₂ and measuring fluorescence, absorption and Electron Spin Resonance (ESR). In this paper, we used indocyanine green (ICG), the only near-infrared (NIR) probe approved by the Food and Drug Administration (FDA), to detect ¹O₂ in vitro. Once it reacts with ¹O₂, ICG is decomposed and its UV absorption at 780 nm decreases with the laser irradiation. Our data demonstrated that ICG could be more sensitive and accurate than Singlet Oxygen Sensor Green reagent(®) (SOSG, a commercialized fluorescence probe) in vitro, moreover, ICG functioned with Eosin Y while SOSG failed. Thus, ICG would reasonably provide the possibility to sense ¹O₂ in vitro, with high sensitivity, selectivity and suitability to most photosensitizers.

No Photon Wasted: An Efficient and Selective Singlet Oxygen Photosensitizing Protein.

PubMed

Westberg, Michael; Bregnhøj, Mikkel; Etzerodt, Michael; Ogilby, Peter R

2017-10-12

Optogenetics has been, and will continue to be, a boon to mechanistic studies of cellular processes. Genetically encodable proteins that sensitize the production of reactive oxygen species (ROS) are expected to play an increasingly important role, particularly in elucidating mechanisms of temporally and spatially dependent cell signaling. However, a substantial challenge in developing such photosensitizing proteins has been to funnel the optical excitation energy into the initial selective production of only one ROS. Singlet molecular oxygen, O 2 (a 1 Δ g ), is a ROS known to have a wide range of effects on cell function. Nevertheless, mechanistic details of singlet oxygen's behavior in a cell are lacking. On the basis of the rational optimization of a LOV-derived flavoprotein, we now report the development and photophysical characterization of a protein-encased photosensitizer that efficiently and selectively produces singlet oxygen at the expense of other ROS, especially ROS that derive from photoinduced electron transfer reactions. These results set the stage for a plethora of new experiments to elucidate ROS-mediated events in cells.

Comparing the efficiency of supersonic oxygen-iodine laser with different mixing designs

NASA Astrophysics Data System (ADS)

Vyskubenko, Boris A.; Adamenkov, A. A.; Bakshin, V. V.; Efremov, V. I.; Ilyin, S. P.; Kolobyanin, Yu. V.; Krukovsky, I. M.; Kudryashov, E. A.; Moiseyev, V. B.

2003-11-01

The paper presents experimental studies of supersonic oxygen-iodine laser (OIL) using twisted-flow singlet oxygen generator (SOG) over a wide range of the singlet oxygen pressures and the buffer gas flow rates. The experiments used different designs of the nozzle unit and mixing system for singlet oxygen and iodine gas with the carrier gas (such as nitrogen or helium). For a wide range of the key parameters, the study looked at the efficiency of supersonic OIL with variation of the singlet oxygen pressure. The measurements were made for different positions of the iodine injection plane with respect to the critical cross-section (both in the subsonic part of the nozzle and in the supersonic flow). The gas pressure at the nozzle unit entry was varied from 50 to 250 Torr. The total pressure loss have been found for different mixing designs. Experimental curves are given for energy performance and chemical efficiency of the supersonic OIL as a function of the key parameters. Comparison is made between the calculated and experimental data. For the optimum conditions of OIL operation, chemical efficiency of 25-30% has been achieved.

Methods of Functionalization of Carbon Nanotubes by Photooxidation

NASA Technical Reports Server (NTRS)

Lebron-Colon, Marisabel (Inventor); Meador, Michael A. (Inventor)

2016-01-01

A method of photooxidizing carbon nanotubes, such as single-walled and multi-walled carbon nanotubes. The nanotubes are purified and dispersed in a solvent, such as n-methyl pyrrolidinone or dimethylformamide. A singlet oxygen sensitizer like Rose Bengal is added to the solution. Oxygen gas is continuously supplied while irradiating the solution while irradiating the solution with ultraviolet light to produce singlet oxygen to oxidize the single-walled carbon nanotubes. Advantageously, the method significantly increases the level of oxidation compared with prior art methods.

Superfluidity in Strongly Interacting Fermi Systems with Applications to Neutron Stars

NASA Astrophysics Data System (ADS)

Khodel, Vladimir

The rotational dynamics and cooling history of neutron stars is influenced by the superfluid properties of nucleonic matter. In this thesis a novel separation technique is applied to the analysis of the gap equation for neutron matter. It is shown that the problem can be recast into two tasks: solving a simple system of linear integral equations for the shape functions of various components of the gap function and solving a system of non-linear algebraic equations for their scale factors. Important simplifications result from the fact that the ratio of the gap amplitude to the Fermi energy provides a small parameter in this problem. The relationship between the analytic structure of the shape functions and the density interval for the existence of superfluid gap is discussed. It is shown that in 1S0 channel the position of the first zero of the shape function gives an estimate of the upper critical density. The relation between the resonant behavior of the two-neutron interaction in this channel and the density dependence of the gap is established. The behavior of the gap in the limits of low and high densities is analyzed. Various approaches to calculation of the scale factors are considered: model cases, angular averaging, and perturbation theory. An optimization-based approach is proposed. The shape functions and scale factors for Argonne υ14 and υ18 potentials are determined in singlet and triplet channels. Dependence of the solution on the value of effective mass and medium polarization is studied.

Molecular structure, spectroscopic (FT-IR, FT Raman, UV, NMR and THz) investigation and hyperpolarizability studies of 3-(2-Chloro-6-fluorophenyl)-1-(2-thienyl) prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Kumar, Rajesh; Kumar, Amit; Deval, Vipin; Gupta, Archana; Tandon, Poonam; Patil, P. S.; Deshmukh, Prathmesh; Chaturvedi, Deepika; Watve, J. G.

2017-02-01

In the present work, a combined experimental and theoretical study on ground state molecular structure, spectroscopic and nonlinear optical properties of the chalcone derivative 3-(2-Chloro-6-fluorophenyl)-1-(2-thienyl) prop-2-en-1-one (2C6F2SC) is reported. Initial geometry generated from single crystal X-ray diffraction parameters was minimized at DFT level employing B3LYP/6-311++G (d,p) without any constraint to the potential energy surface. The molecule has been characterized using various experimental techniques FT-IR, FT-Raman, UV-Vis, 1H NMR, TD-THz and the spectroscopic data have been analyzed theoretically by Density Functional Theory (DFT) method. Harmonic vibrational frequencies were calculated theoretically using the optimized ground state geometry and the spectra were interpreted by means of potential energy distribution. Time Dependent Density Functional Theory (TD-DFT) has been used to calculate energies, absorption wavelengths, oscillator strengths of electronic singlet-singlet transitions. The calculated energy and oscillator strength complement with the experimental findings. The HOMO-LUMO energy gap explains the charge interaction taking place within the molecule. Good correlations between the experimental 1H NMR chemical shifts and calculated GIAO shielding tensors were found. Stability of the molecule, hyperconjugative interactions and charge delocalization has been analyzed by natural bond orbital (NBO) analysis. The first order hyperpolarizability (β) of this molecular system and related properties (μ, <α> and Δα) have been calculated using the finite-field approach.

Electron impact excitation of the merocyanine molecule in the gas phase

NASA Astrophysics Data System (ADS)

Kulinich, A. V.; Ishchenko, A. A.; Kukhta, I. N.; Mitryukhin, L. K.; Kazakov, S. M.; Kukhta, A. V.

2018-03-01

Electronic transitions in a merocyanine dye were studied in the gas phase using electron energy loss spectroscopy and compared with the optical absorption spectra. It was found that the most intense band of the S1 ← S0 polymethine transition lies at 2.8 eV in vapor and 2.4 eV in n-hexane. Higher electronic transitions in the range of 3.7-7 eV were also analyzed. Besides, the singlet-triplet transition was revealed near 1.8 eV. TDDFT simulation of singlet-singlet transitions in the studied molecule was performed using B97D3, B3LYP, B3PW91 and wB97xD functionals. The calculated energy of the long-wavelength transition is closest to the experimental value with the latter. Other functionals result in the energy 0.2-0.4 eV exceeding experimental. The interpretation of higher transitions/bands is complicated due to their superposition and difference between experimental and calculated data. The excitation anisotropy spectra were measured in glycerol for more reliable determination of higher transitions and comparison with the TDDFT/PCM simulation.

MC-PDFT can calculate singlet-triplet splittings of organic diradicals

NASA Astrophysics Data System (ADS)

Stoneburner, Samuel J.; Truhlar, Donald G.; Gagliardi, Laura

2018-02-01

The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT), and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT. It is also shown that MC-PDFT is much less computationally expensive than CASPT2 when applied to larger active spaces, and this illustrates the promise of this method for larger diradical organic systems.

Masses of Open-Flavour Heavy-Light Hybrids from QCD Sum Rules

NASA Astrophysics Data System (ADS)

Ho, Jason; Harnett, Derek; Steele, Tom

2017-01-01

Our current understanding of the strong interaction (QCD) permits the construction of colour singlet states with novel structures that do not fit within the traditional quark model, including hybrid mesons. To date, though other exotic structures such as pentaquark and tetraquark states have been confirmed, no unambiguous hybrid meson signals have been observed. However, with data collection at the GlueX experiment ongoing and with the construction of the PANDA experiment at FAIR, the opportunity to observe hybrid states has never been better. As theoretical calculations are a necessary piece for the identification of any observed experimental resonance, we present our mass predictions of heavy-light open-flavour hybrid mesons using QCD Laplace sum-rules for all scalar and vector JP channels, and including non-perturbative condensate contributions up to six-dimensions.

A Conserved Structural Module Regulates Transcriptional Responses to Diverse Stress Signals in Bacteria

PubMed Central

Campbell, Elizabeth A.; Greenwell, Roger; Anthony, Jennifer R.; Wang, Sheng; Lim, Lionel; Das, Kalyan; Sofia, Heidi J.; Donohue, Timothy J.; Darst, Seth A.

2008-01-01

SUMMARY A transcriptional response to singlet oxygen in Rhodobacter sphaeroides is controlled by the group IV σ factor σE and its cognate anti-σ ChrR. Crystal structures of the σE/ChrR complex reveal a modular, two-domain architecture for ChrR. The ChrR N-terminal anti-σ domain (ASD) binds a Zn2+ ion, contacts σE, and is sufficient to inhibit σE-dependent transcription. The ChrR C-terminal domain adopts a cupin fold, can coordinate an additional Zn2+, and is required for the transcriptional response to singlet oxygen. Structure-based sequence analyses predict that the ASD defines a common structural fold among predicted group IV antiσs. These ASDs are fused to diverse C-terminal domains that are likely involved in responding to specific environmental signals that control the activity of their cognate σ factor. PMID:17803943

The crystal structure of a cyanobacterial water-soluble carotenoid binding protein.

PubMed

Kerfeld, Cheryl A; Sawaya, Michael R; Brahmandam, Vishnu; Cascio, Duilio; Ho, Kwok Ki; Trevithick-Sutton, Colleen C; Krogmann, David W; Yeates, Todd O

2003-01-01

Carotenoids undergo a wide range of photochemical reactions in animal, plant, and microbial systems. In photosynthetic organisms, in addition to light harvesting, they perform an essential role in protecting against light-induced damage by quenching singlet oxygen, superoxide anion radicals, or triplet-state chlorophyll. We have determined the crystal structure of a water-soluble orange carotenoid protein (OCP) isolated from the cyanobacterium Arthrospira maxima at a resolution of 2.1 A. OCP forms a homodimer with one carotenoid molecule per monomer. The carotenoid binding site is lined by a striking number of methionine residues. The structure reveals several possible ways in which the protein environment influences the spectral properties of the pigment and provides insight into how the OCP carries out its putative functions in photoprotection.

A Variational Monte Carlo Approach to Atomic Structure

ERIC Educational Resources Information Center

Davis, Stephen L.

2007-01-01

The practicality and usefulness of variational Monte Carlo calculations to atomic structure are demonstrated. It is found to succeed in quantitatively illustrating electron shielding, effective nuclear charge, l-dependence of the orbital energies, and singlet-tripetenergy splitting and ionization energy trends in atomic structure theory.

Quenching of fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules

NASA Astrophysics Data System (ADS)

Bagnich, S. A.; Knyukshto, V. N.

2006-11-01

We have studied the mechanisms for quenching of the fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules. We have shown that molecules in the diketone series are quenching agents for the fluorescence of the indicated polymers, and can serve as singlet-triplet converters capable of populating the triplet state of the polymer. We have observed that the efficiency of quenching of the fluorescence of the studied polymers depends considerably on the presence of bulky side groups in the polymer or in the activator molecules. Based on analysis of the data obtained, we conclude that in the case of a rigid planar structure for the polymer, a significant contribution to quenching of its fluorescence comes from not only singlet-singlet energy transfer but also charge transfer, leading to formation of intermolecular complexes (exciplexes).

Deviation pattern approach for optimizing perturbative terms of QCD renormalization group invariant observables

NASA Astrophysics Data System (ADS)

Khellat, M. R.; Mirjalili, A.

2017-03-01

We first consider the idea of renormalization group-induced estimates, in the context of optimization procedures, for the Brodsky-Lepage-Mackenzie approach to generate higher-order contributions to QCD perturbative series. Secondly, we develop the deviation pattern approach (DPA) in which through a series of comparisons between lowerorder RG-induced estimates and the corresponding analytical calculations, one could modify higher-order RG-induced estimates. Finally, using the normal estimation procedure and DPA, we get estimates of αs4 corrections for the Bjorken sum rule of polarized deep-inelastic scattering and for the non-singlet contribution to the Adler function.

Investigating plausible mechanisms for the photo-induced partial unfolding of a globular protein

NASA Astrophysics Data System (ADS)

Parker, James E.

Two hypotheses are proposed to explain the photo-induced unfolding of β-lactoglobulin (BLG) that occurs when non-covalently bound to a dye molecule, meso-tetrakis (p-sulfonatophenyl) porphyrin (TSPP), and illuminated by a laser in the post-Tanford transition configuration. The first involves a photo-induced electron transfer from the porphyrin to the protein. The second involves the production of kynurenine by singlet oxygen that is generated during photo-excitation of the porphyrin. To evaluate these hypotheses, a series of computational and experimental results have been combined to establish the physical state of the BLG-TSPP complex and to estimate the likelihood of a post-irradiation event to initiate the partial unfolding. Determining the binding site location is crucial to establish the position of the photo-induced events and the likely end-product. A study of the vibronic state of the BLG-TSPP complex using resonant Raman and absorption spectroscopy coupled with density functional theory (DFT) and docking simulations is used to estimate the location of the binding site. Once the binding site is found, molecular dynamics simulations of the post-irradiation event relaxations in the protein are used to estimate the resulting secondary structure. This structure is compared to experimental estimates of the secondary structure of the unfolded protein to determine which hypothesis is the most likely mechanism to explain the unfolding.

Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity

PubMed Central

Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

2016-01-01

Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen. PMID:27622274

LuAG:Pr3+-porphyrin based nanohybrid system for singlet oxygen production: Toward the next generation of PDTX drugs.

PubMed

Popovich, Kseniya; Tomanová, Kateřina; Čuba, Václav; Procházková, Lenka; Pelikánová, Iveta Terezie; Jakubec, Ivo; Mihóková, Eva; Nikl, Martin

2018-02-01

A highly prospective drug for the X-ray induced photodynamic therapy (PDTX), LuAG:Pr 3+ @SiO 2 -PpIX nanocomposite, was successfully prepared by a three step process: photo-induced precipitation of the Lu 3 Al 5 O 12 :Pr 3+ (LuAG:Pr 3+ ) core, sol-gel technique for amorphous silica coating, and a biofunctionalization by attaching the protoporphyrin IX (PpIX) molecules. The synthesis procedure provides three-layer nanocomposite with uniform shells covering an intensely luminescent core. Room temperature radioluminescence (RT RL) spectra as well as photoluminescence (RT PL) steady-state and time resolved spectra of the material confirm the non-radiative energy transfer from the core Pr 3+ ions to the PpIX outer layer. First, excitation of Pr 3+ ions results in the red luminescence of PpIX. Second, the decay measurements exhibit clear evidence of mentioned non-radiative energy transfer (ET). The singlet oxygen generation in the system was demonstrated by the 3'-(p-aminophenyl) fluorescein (APF) chemical probe sensitive to the singlet oxygen presence. The RT PL spectra of an X-ray irradiated material with the APF probe manifest the formation of singlet oxygen due to which enhanced luminescence around 530 nm is observed. Quenching studies, using NaN 3 as an 1 O 2 inhibitor, also confirm the presence of 1 O 2 in the system and rule out the parasitic reaction with OH radicals. To summarize, presented features of LuAG:Pr 3+ @SiO 2 -PpIX nanocomposite indicate its considerable potential for PDTX application. Copyright © 2018 Elsevier B.V. All rights reserved.

Laser pulse induced multi-exciton dynamics in molecular systems

NASA Astrophysics Data System (ADS)

Wang, Luxia; May, Volkhard

2018-03-01

Ultrafast optical excitation of an arrangement of identical molecules is analyzed theoretically. The computations are particularly dedicated to molecules where the excitation energy into the second excited singlet state E(S 2) - E(S 0) is larger than twice the excitation energy into the first excited singlet state E(S 1) - E(S 0). Then, exciton-exciton annihilation is diminished and resonant and intensive excitation may simultaneously move different molecules into their first excited singlet state | {S}1> . To describe the temporal evolution of the thus created multi-exciton state a direct computation of the related wave function is circumvented. Instead, we derive equations of motion for expectation values formed by different arrangements of single-molecule transition operators | {S}1> < {S}0| . First simulation results are presented and the approximate treatment suggested recently in 2016 Phys. Rev. B 94 195413 is evaluated.

Experimental Energy Levels and Partition Function of the 12C2 Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szabó, István; Császár, Attila G.; Bernath, Peter F.; Yurchenko, Sergei N.; Tennyson, Jonathan

2016-06-01

The carbon dimer, the 12C2 molecule, is ubiquitous in astronomical environments. Experimental-quality rovibronic energy levels are reported for 12C2, based on rovibronic transitions measured for and among its singlet, triplet, and quintet electronic states, reported in 42 publications. The determination utilizes the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. The 23,343 transitions measured experimentally and validated within this study determine 5699 rovibronic energy levels, 1325, 4309, and 65 levels for the singlet, triplet, and quintet states investigated, respectively. The MARVEL analysis provides rovibronic energies for six singlet, six triplet, and two quintet electronic states. For example, the lowest measurable energy level of the {{a}}{}3{{{\\Pi }}}{{u}} state, corresponding to the J = 2 total angular momentum quantum number and the F 1 spin-multiplet component, is 603.817(5) cm-1. This well-determined energy difference should facilitate observations of singlet-triplet intercombination lines, which are thought to occur in the interstellar medium and comets. The large number of highly accurate and clearly labeled transitions that can be derived by combining MARVEL energy levels with computed temperature-dependent intensities should help a number of astrophysical observations as well as corresponding laboratory measurements. The experimental rovibronic energy levels, augmented, where needed, with ab initio variational ones based on empirically adjusted and spin-orbit coupled potential energy curves obtained using the Duo code, are used to obtain a highly accurate partition function, and related thermodynamic data, for 12C2 up to 4000 K.

Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”

DOE PAGES

Moore, II, Barry; Schrader, Robert L.; Kowalski, Karol; ...

2017-05-02

The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals ledmore » to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.« less

Accurate simulation of geometry, singlet-singlet and triplet-singlet excitation of cyclometalated iridium(III) complex.

PubMed

Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Zhang, Hong-Xing; Cui, Tian

2014-03-01

In the current contribution, we present a critical study of the theoretical protocol used for the determination of the electronic spectra properties of luminescent cyclometalated iridium(III) complex, [Ir(III)(ppy)₂H₂dcbpy]⁺ (where, ppy = 2-phenylpyridine, H₂dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid), considered as a representative example of the various problems related to the prediction of electronic spectra of transition metal complex. The choice of the exchange-correlation functional is crucial for the validity of the conclusions that would be drawn from the numerical results. The influence of the exchange-correlation on geometry parameter and absorption/emission band, the role of solvent effects on time-dependent density function theory (TD-DFT) calculations, as well as the importance of the chosen proper procedure to optimize triplet excited geometry, have been thus examined in detail. From the obtained results, some general conclusions and guidelines are presented: i) PBE0 functional is the most accurate in prediction of ground state geometry; ii) the well-established B3LYP, B3P86, PBE0, and X3LYP have similar accuracy in calculation of absorption spectrum; and iii) the hybrid approach TD-DFT//CIS gives out excellent agreement in the evaluation of triplet excitation energy.

Photoprotection and triplet energy transfer in higher plants: the role of electronic and nuclear fluctuations.

PubMed

Cupellini, Lorenzo; Jurinovich, Sandro; Prandi, Ingrid G; Caprasecca, Stefano; Mennucci, Benedetta

2016-04-28

Photosynthetic organisms employ several photoprotection strategies to avoid damage due to the excess energy in high light conditions. Among these, quenching of triplet chlorophylls by neighboring carotenoids (Cars) is fundamental in preventing the formation of singlet oxygen. Cars are able to accept the triplets from chlorophylls by triplet energy transfer (TET). We have here studied TET rates in CP29, a minor light-harvesting complex (LHC) of the Photosystem II in plants. A fully atomistic strategy combining classical molecular dynamics of the LHC in its natural environment with a hybrid time-dependent density functional theory/polarizable MM description of the TET is used. We find that the structural fluctuations of the pigment-protein complex can largely enhance the transfer rates with respect to those predicted using the crystal structure, reducing the triplet quenching times in the subnanosecond scale. These findings add a new perspective for the interpretation of the photoprotection function and its relation with structural motions of the LHC.

Staggered fermions, zero modes, and flavor-singlet mesons

DOE PAGES

Donald, Gordon C; Davies, Christine T.H.; Follana, Eduardo; ...

2011-09-12

We examine the taste structure of eigenvectors of the staggered-fermion Dirac operator. We derive a set of conditions on the eigenvectors of modes with small eigenvalues (near-zero modes), such that staggered fermions reproduce the 't Hooft vertex in the continuum limit. We also show that, assuming these conditions, the correlators of flavor-singlet mesons are free of contributions singular in 1/m, where m is the quark mass. This conclusion holds also when a single flavor of sea quark is represented by the fourth root of the staggered-fermion determinant. We then test numerically, using the HISQ action, whether these conditions hold onmore » realistic lattice gauge fields. We find that the needed structure does indeed emerge.« less

Photophysical and photochemical properties of Bauhinia megalandra (Caesalpinaceae) extracts as new PDT photosensitizer

NASA Astrophysics Data System (ADS)

Vargas Tovar, Franklin R.; Rivas, C.; Estrada, O.; Marcano O., Aristides A.; Echevarria, Lorenzo; Diaz, Yrene; Alexander, I.; Rodriguez, L.; Padron, L.; Rivera, I. R.

2004-10-01

Recently new photosensitizers, chlorophyll "a and b" derivatives, for photodynamic therapy (PDT) have been presented. It already passed complete pre-clinical investigations. This prompted us to carry out an extensive study of photophysical properties of chlorine derivatives, important both for optimization of their clinic applications and for study of mechanisms of chlorine PDT&. The fresh leaves of Bauhinia megalandra (Caesalpinaceae) were extracted with methanol by percolation, and re-extract with a mixture of methanol-water (1:1), the insoluble fraction was then separated by column chromatography [RP18/hexane-ethylacetate (9:1)] to obtain four fractions named 1 to 4. These compounds were identified by NMR data. We found that 3 and 4 efficiently generates singlet oxygen when irradiated with visible light. Detection of the singlet oxygen was fulfilled by its reaction with histidine and detected by bleaching p-nitrosodimethylaniline under 440 nm irradiation. The quantum yields of singlet oxygen determined by us were 0.088 (1), 0.151 (2), 0.219 (3) and 0.301 (4). We measured absorption and fluorescence spectra of compounds 1 to 4 (Mg-chlorophyll-a, Pheophytin, Mg-chlorophyll-b and chlorophyll-b respectively) in different media and in aqueous solutions of human serum albumin. The association constant of the compounds 1, 2, 3 and 4 in the presence of HSA were estimated. The binding and quenching studies suggest that only 1 and 3 may serve as a useful fluorescence probe for structure/function studies of different chlorophyll binding proteins. No photoinduced binding was observed after irradiation by all the studied compounds in presence of human serum albumin.

The Non-Adiabatic dynamics of Singlet Fission in Polyacenes

NASA Astrophysics Data System (ADS)

Bradforth, Stephen

2015-03-01

Singlet fission involves the splitting of a single excitation into two coupled triplet excitations and is manifested in an increasing range of aromatic crystals and amorphous thin films. If the energy of the lowest triplet state is one half (or less) of the first singlet excited state, as it is for tetracene or pentacene and their derivatives, singlet fission may occur between two adjacent chromophores. Since there is no change in the overall spin state of the system, singlet fission can be exceptionally fast, occuring on the fs - ps range. If the triplets can diffuse away from the fission site they are available for harvesting as a dissociated carriers with up to two charge carrier pairs per absorbed photon. The possibility of recovering excess energy above the material band gap (in this case determined by the triplet energy) when a higher energy photon is absorbed has led to great recent interest in exploiting this process for increased efficiency solar energy harvesting. The nature of the electronic couplings between the chromophores, intermediate electronic configurations, and the role of entropy in the spin-allowed primary fission event have all come under great scrutiny. Results from a series of femtosecond spectroscopy experiments on a variety of amorphous thin films, nanoparticles and isolated acene dimer compounds will be presented that shed light on the electronic intermediate states key to the efficiency and speed of this process. Work supported as part of the Center for Energy Nanoscience, an Energy Frontier Research Center funded by the U.S. Department of Energy (DE-SC0001013).

Static Holes in Geometrically Frustrated Bow Tie Ladder

NASA Astrophysics Data System (ADS)

Martins, George; Brenig, Wolfram

2007-03-01

Doping of the geometrically frustrated bow-tie spin ladder with static holes is investigated by a complementary approach using exact diagonalization and hard-core quantum dimers. Results for the thermodynamics in the undoped case, the singlet density of states, the hole-binding energy, and the spin correlations will be presented. We find that the static holes polarize their vicinity by a localization of singlets in order to reduce the frustration. As a consequence the singlet polarization cloud induces short range repulsive forces between the holes with oscillatory longer range behavior. For those systems we have studied, most results for the quantum dimer approach are found to be qualitatively if not quantitatively in agreement with exact diagonalization. The ground state of the undoped system is non-degenerate with translationally invariant nearest-neighbor spin correlations up to a few unit cells, which is consistent with a spin liquid state or a valence bond crystal with very large unit cell. C. Waldtmann, A. Kreutzmann, U. Schollwock, K. Maisinger, and H.-U. Everts, Phys. Rev. B 62, 9472 (2000).

The mechanism of oxidation in chromophore maturation of wild-type green fluorescent protein: a theoretical study.

PubMed

Ma, Yingying; Sun, Qiao; Smith, Sean C

2017-05-24

Oxidation is viewed as the second and rate-limiting step in the chromophore maturation process of the wild-type green fluorescent protein (GFP) under aerobic conditions. Molecular oxygen is the necessary oxidant for GFP chromophore biosynthesis. In this study, density functional theory (DFT) calculations were employed to study the mechanism of oxidation. Our results indicate that the deprotonation of the Tyr66 α-carbon is probably the rate-limiting step in the oxidation step. Electron transfer from the enolate form of the five-membered heterocycle (EFMH) to molecular oxygen, generating the triplet radical complex [EFMH˙O 2 - ˙] T , is an important step. This complex undergoes intersystem crossing to form an open-shell singlet diradical complex before it forms the closed-shell singlet hydroperoxy adduct. The formation of the hydroperoxy adduct is a proton-coupled electron transfer process. The energy barrier of H 2 O 2 elimination is 16.5 kcal mol -1 . The oxidation product IFMHH 2 O 2 that we discovered is a hydroxylated cyclic imine structure, which is consistent with the crystal structure trapped in the colorless Y66L variant. The relative energy of the oxidation product is -48.7 kcal mol -1 , which is in accordance with the experimental observation that the thermodynamically unfavourable cyclized product is trapped by oxidation. The results herein support the cyclization-oxidation-dehydration mechanism for the chromophore maturation of GFP.

Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? The Silicon (Si(3P))-Dimethylacetylene (C4H6(X1A1g)) System as a Case Study.

PubMed

Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H

2018-06-06

The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.

Spin Contamination Error in Optimized Geometry of Singlet Carbene (1A1) by Broken-Symmetry Method

NASA Astrophysics Data System (ADS)

Kitagawa, Yasutaka; Saito, Toru; Nakanishi, Yasuyuki; Kataoka, Yusuke; Matsui, Toru; Kawakami, Takashi; Okumura, Mitsutaka; Yamaguchi, Kizashi

2009-10-01

Spin contamination errors of a broken-symmetry (BS) method in optimized structural parameters of the singlet methylene (1A1) molecule are quantitatively estimated for the Hartree-Fock (HF) method, post-HF methods (CID, CCD, MP2, MP3, MP4(SDQ)), and a hybrid DFT (B3LYP) method. For the purpose, the optimized geometry by the BS method is compared with that of an approximate spin projection (AP) method. The difference between the BS and the AP methods is about 10-20° in the HCH angle. In order to examine the basis set dependency of the spin contamination error, calculated results by STO-3G, 6-31G*, and 6-311++G** are compared. The error depends on the basis sets, but the tendencies of each method are classified into two types. Calculated energy splitting values between the triplet and the singlet states (ST gap) indicate that the contamination of the stable triplet state makes the BS singlet solution stable and the ST gap becomes small. The energy order of the spin contamination error in the ST gap is estimated to be 10-1 eV.

Pentacene Dimers as a Critical Tool for the Investigation of Intramolecular Singlet Fission.

PubMed

Hetzer, Constantin; Guldi, Dirk M; Tykwinski, Rik R

2018-01-11

Singlet fission (SF) involves the spontaneous splitting of a photoexcited singlet state into a pair of triplets, and it holds great promise toward the realization of more efficient solar cells. Although the process of SF has been known since the 1960s, debate regarding the underlying mechanism continues to this day, especially for molecular materials. A number of different chromophores have been synthesized and studied in order to better understand the process of SF. These previous reports have established that pentacene and its derivatives are especially well-suited for the study of SF, since the energetic requirement E(S 1 )≥2E(T 1 ) is fulfilled rendering the process exothermic and unidirectional. Dimeric pentacene derivatives, in which individual pentacene chromophores are tethered by a "spacer", have emerged as the system of choice toward exploring the mechanism of intramolecular singlet fission (iSF). The dimeric structure, and in particular the spacer, allows for controlling and tuning the distance, geometric relationship, and electronic coupling between the two pentacene moieties. This Minireview describes recent advances using pentacene dimers for the investigation of iSF. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zafra, José Luis; González Cano, Rafael C.; Ruiz Delgado, M. Carmen

A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing tomore » singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.« less

Photosensitized degradation of losartan potassium in an extemporaneous suspension formulation.

PubMed

Seburg, Randal A; Ballard, John M; Hwang, Tsang-Lin; Sullivan, Caitlin M

2006-10-11

During development of an extemporaneous suspension formulation for losartan potassium, previously unknown degradation products were observed in experimental suspensions prepared in a commercial cherry syrup vehicle. These degradates increased rapidly when analytical solutions prepared from that suspension were exposed to ambient light. The structures of the degradates were determined using a combination of preparative HPLC, LC/MS, (13)C and (1)H NMR (1D and 2D), and mechanistic chemistry. Each degradate results from destruction of the imidazole ring of losartan. Formation of the two major degradates required exposure to light (UV or visible) and the presence of oxygen. Experiments using Rose Bengal (a singlet oxygen photosensitizer) and 1,4-diazabicyclooctane (DABCO; a singlet oxygen quencher) established that the major photodegradates are formed via the intermediacy of singlet oxygen. The identity of the photosensitizer in the formulation was not unequivocally determined; however, the experiments implicated the artificial flavoring in fulfilling this role.

Measurement of the differential cross-sections of inclusive, prompt and non-prompt J/ψ production in proton-proton collisions at √{s}=7 TeV

NASA Astrophysics Data System (ADS)

Aad, G.; Abbott, B.; Abdallah, J.; Abdelalim, A. A.; Abdesselam, A.; Abdinov, O.; Abi, B.; Abolins, M.; Abramowicz, H.; Abreu, H.; Acerbi, E.; Acharya, B. S.; Adams, D. L.; Addy, T. N.; Adelman, J.; Aderholz, M.; Adomeit, S.; Adragna, P.; Adye, T.; Aefsky, S.; Aguilar-Saavedra, J. A.; Aharrouche, M.; Ahlen, S. P.; Ahles, F.; Ahmad, A.; Ahsan, M.; Aielli, G.; Akdogan, T.; Åkesson, T. P. A.; Akimoto, G.; Akimov, A. V.; Akiyama, A.; Alam, M. S.; Alam, M. A.; Albrand, S.; Aleksa, M.; Aleksandrov, I. N.; Aleppo, M.; Alessandria, F.; Alexa, C.; Alexander, G.; Alexandre, G.; Alexopoulos, T.; Alhroob, M.; Aliev, M.; Alimonti, G.; Alison, J.; Aliyev, M.; Allport, P. P.; Allwood-Spiers, S. E.; Almond, J.; Aloisio, A.; Alon, R.; Alonso, A.; Alviggi, M. G.; Amako, K.; Amaral, P.; Amelung, C.; Ammosov, V. V.; Amorim, A.; Amorós, G.; Amram, N.; Anastopoulos, C.; Andeen, T.; Anders, C. F.; Anderson, K. J.; Andreazza, A.; Andrei, V.; Andrieux, M.-L.; Anduaga, X. S.; Angerami, A.; Anghinolfi, F.; Anjos, N.; Annovi, A.; Antonaki, A.; Antonelli, M.; Antonelli, S.; Antonov, A.; Antos, J.; Anulli, F.; Aoun, S.; Aperio Bella, L.; Apolle, R.; Arabidze, G.; Aracena, I.; Arai, Y.; Arce, A. T. H.; Archambault, J. P.; Arfaoui, S.; Arguin, J.-F.; Arik, E.; Arik, M.; Armbruster, A. J.; Arnaez, O.; Arnault, C.; Artamonov, A.; Artoni, G.; Arutinov, D.; Asai, S.; Asfandiyarov, R.; Ask, S.; Åsman, B.; Asquith, L.; Assamagan, K.; Astbury, A.; Astvatsatourov, A.; Atoian, G.; Aubert, B.; Auerbach, B.; Auge, E.; Augsten, K.; Aurousseau, M.; Austin, N.; Avramidou, R.; Axen, D.; Ay, C.; Azuelos, G.; Azuma, Y.; Baak, M. A.; Baccaglioni, G.; Bacci, C.; Bach, A. M.; Bachacou, H.; Bachas, K.; Bachy, G.; Backes, M.; Backhaus, M.; Badescu, E.; Bagnaia, P.; Bahinipati, S.; Bai, Y.; Bailey, D. C.; Bain, T.; Baines, J. T.; Baker, O. K.; Baker, M. D.; Baker, S.; Baltasar Dos Santos Pedrosa, F.; Banas, E.; Banerjee, P.; Banerjee, Sw.; Banfi, D.; Bangert, A.; Bansal, V.; Bansil, H. S.; Barak, L.; Baranov, S. P.; Barashkou, A.; Barbaro Galtieri, A.; Barber, T.; Barberio, E. L.; Barberis, D.; Barbero, M.; Bardin, D. Y.; Barillari, T.; Barisonzi, M.; Barklow, T.; Barlow, N.; Barnett, B. M.; Barnett, R. M.; Baroncelli, A.; Barr, A. J.; Barreiro, F.; Barreiro Guimarães da Costa, J.; Barrillon, P.; Bartoldus, R.; Barton, A. E.; Bartsch, D.; Bartsch, V.; Bates, R. L.; Batkova, L.; Batley, J. R.; Battaglia, A.; Battistin, M.; Battistoni, G.; Bauer, F.; Bawa, H. S.; Beare, B.; Beau, T.; Beauchemin, P. H.; Beccherle, R.; Bechtle, P.; Beck, H. P.; Beckingham, M.; Becks, K. H.; Beddall, A. J.; Beddall, A.; Bedikian, S.; Bednyakov, V. A.; Bee, C. P.; Begel, M.; Behar Harpaz, S.; Behera, P. K.; Beimforde, M.; Belanger-Champagne, C.; Bell, P. J.; Bell, W. H.; Bella, G.; Bellagamba, L.; Bellina, F.; Bellomo, G.; Bellomo, M.; Belloni, A.; Beloborodova, O.; Belotskiy, K.; Beltramello, O.; Ben Ami, S.; Benary, O.; Benchekroun, D.; Benchouk, C.; Bendel, M.; Benedict, B. H.; Benekos, N.; Benhammou, Y.; Benjamin, D. P.; Benoit, M.; Bensinger, J. R.; Benslama, K.; Bentvelsen, S.; Berge, D.; Bergeaas Kuutmann, E.; Berger, N.; Berghaus, F.; Berglund, E.; Beringer, J.; Bernardet, K.; Bernat, P.; Bernhard, R.; Bernius, C.; Berry, T.; Bertinelli, F.; Bertolucci, F.; Besana, M. I.; Besson, N.; Bethke, S.; Bhimji, W.; Bianchi, R. M.; Bianco, M.; Biebel, O.; Bieniek, S. P.; Biesiada, J.; Biglietti, M.; Bilokon, H.; Bindi, M.; Binet, S.; Bingul, A.; Bini, C.; Biscarat, C.; Bitenc, U.; Black, K. M.; Blair, R. E.; Blanchard, J.-B.; Blanchot, G.; Blocker, C.; Blocki, J.; Blondel, A.; Blum, W.; Blumenschein, U.; Bobbink, G. J.; Bobrovnikov, V. B.; Bocci, A.; Boddy, C. R.; Boehler, M.; Boek, J.; Boelaert, N.; Böser, S.; Bogaerts, J. 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G.; Searcy, J.; Sedykh, E.; Segura, E.; Seidel, S. C.; Seiden, A.; Seifert, F.; Seixas, J. M.; Sekhniaidze, G.; Seliverstov, D. M.; Sellden, B.; Sellers, G.; Seman, M.; Semprini-Cesari, N.; Serfon, C.; Serin, L.; Seuster, R.; Severini, H.; Sevior, M. E.; Sfyrla, A.; Shabalina, E.; Shamim, M.; Shan, L. Y.; Shank, J. T.; Shao, Q. T.; Shapiro, M.; Shatalov, P. B.; Shaver, L.; Shaw, C.; Shaw, K.; Sherman, D.; Sherwood, P.; Shibata, A.; Shimizu, S.; Shimojima, M.; Shin, T.; Shmeleva, A.; Shochet, M. J.; Short, D.; Shupe, M. A.; Sicho, P.; Sidoti, A.; Siebel, A.; Siegert, F.; Siegrist, J.; Sijacki, Dj.; Silbert, O.; Silva, J.; Silver, Y.; Silverstein, D.; Silverstein, S. B.; Simak, V.; Simard, O.; Simic, Lj.; Simion, S.; Simmons, B.; Simonyan, M.; Sinervo, P.; Sinev, N. B.; Sipica, V.; Siragusa, G.; Sisakyan, A. N.; Sivoklokov, S. Yu.; Sjölin, J.; Sjursen, T. B.; Skinnari, L. A.; Skovpen, K.; Skubic, P.; Skvorodnev, N.; Slater, M.; Slavicek, T.; Sliwa, K.; Sloan, T. J.; Sloper, J.; Smakhtin, V.; Smirnov, S. Yu.; Smirnova, L. N.; Smirnova, O.; Smith, B. C.; Smith, D.; Smith, K. M.; Smizanska, M.; Smolek, K.; Snesarev, A. A.; Snow, S. W.; Snow, J.; Snuverink, J.; Snyder, S.; Soares, M.; Sobie, R.; Sodomka, J.; Soffer, A.; Solans, C. A.; Solar, M.; Solc, J.; Soldatov, E.; Soldevila, U.; Solfaroli Camillocci, E.; Solodkov, A. A.; Solovyanov, O. V.; Sondericker, J.; Soni, N.; Sopko, V.; Sopko, B.; Sorbi, M.; Sosebee, M.; Soukharev, A.; Spagnolo, S.; Spanò, F.; Spighi, R.; Spigo, G.; Spila, F.; Spiriti, E.; Spiwoks, R.; Spousta, M.; Spreitzer, T.; Spurlock, B.; St. Denis, R. D.; Stahl, T.; Stahlman, J.; Stamen, R.; Stanecka, E.; Stanek, R. W.; Stanescu, C.; Stapnes, S.; Starchenko, E. A.; Stark, J.; Staroba, P.; Starovoitov, P.; Staude, A.; Stavina, P.; Stavropoulos, G.; Steele, G.; Steinbach, P.; Steinberg, P.; Stekl, I.; Stelzer, B.; Stelzer, H. J.; Stelzer-Chilton, O.; Stenzel, H.; Stevenson, K.; Stewart, G. A.; Stillings, J. A.; Stockmanns, T.; Stockton, M. C.; Stoerig, K.; Stoicea, G.; Stonjek, S.; Strachota, P.; Stradling, A. R.; Straessner, A.; Strandberg, J.; Strandberg, S.; Strandlie, A.; Strang, M.; Strauss, E.; Strauss, M.; Strizenec, P.; Ströhmer, R.; Strom, D. M.; Strong, J. A.; Stroynowski, R.; Strube, J.; Stugu, B.; Stumer, I.; Stupak, J.; Sturm, P.; Soh, D. A.; Su, D.; Subramania, H. S.; Sugaya, Y.; Sugimoto, T.; Suhr, C.; Suita, K.; Suk, M.; Sulin, V. V.; Sultansoy, S.; Sumida, T.; Sun, X.; Sundermann, J. E.; Suruliz, K.; Sushkov, S.; Susinno, G.; Sutton, M. R.; Suzuki, Y.; Sviridov, Yu. M.; Swedish, S.; Sykora, I.; Sykora, T.; Szeless, B.; Sánchez, J.; Ta, D.; Tackmann, K.; Taffard, A.; Tafirout, R.; Taga, A.; Taiblum, N.; Takahashi, Y.; Takai, H.; Takashima, R.; Takeda, H.; Takeshita, T.; Talby, M.; Talyshev, A.; Tamsett, M. C.; Tanaka, J.; Tanaka, R.; Tanaka, S.; Tanaka, S.; Tanaka, Y.; Tani, K.; Tannoury, N.; Tappern, G. P.; Tapprogge, S.; Tardif, D.; Tarem, S.; Tarrade, F.; Tartarelli, G. F.; Tas, P.; Tasevsky, M.; Tassi, E.; Tatarkhanov, M.; Taylor, C.; Taylor, F. E.; Taylor, G. N.; Taylor, W.; Teixeira Dias Castanheira, M.; Teixeira-Dias, P.; Temming, K. K.; Ten Kate, H.; Teng, P. K.; Terada, S.; Terashi, K.; Terron, J.; Terwort, M.; Testa, M.; Teuscher, R. J.; Tevlin, C. M.; Thadome, J.; Therhaag, J.; Theveneaux-Pelzer, T.; Thioye, M.; Thoma, S.; Thomas, J. P.; Thompson, E. N.; Thompson, P. D.; Thompson, P. D.; Thompson, A. S.; Thomson, E.; Thomson, M.; Thun, R. P.; Tic, T.; Tikhomirov, V. O.; Tikhonov, Y. A.; Timmermans, C. J. W. P.; Tipton, P.; Tique Aires Viegas, F. J.; Tisserant, S.; Tobias, J.; Toczek, B.; Todorov, T.; Todorova-Nova, S.; Toggerson, B.; Tojo, J.; Tokár, S.; Tokunaga, K.; Tokushuku, K.; Tollefson, K.; Tomoto, M.; Tompkins, L.; Toms, K.; Tonazzo, A.; Tong, G.; Tonoyan, A.; Topfel, C.; Topilin, N. D.; Torchiani, I.; Torrence, E.; Torró Pastor, E.; Toth, J.; Touchard, F.; Tovey, D. R.; Traynor, D.; Trefzger, T.; Treis, J.; Tremblet, L.; Tricoli, A.; Trigger, I. M.; Trincaz-Duvoid, S.; Trinh, T. N.; Tripiana, M. F.; Triplett, N.; Trischuk, W.; Trivedi, A.; Trocmé, B.; Troncon, C.; Trottier-McDonald, M.; Trzupek, A.; Tsarouchas, C.; Tseng, J. C.-L.; Tsiakiris, M.; Tsiareshka, P. V.; Tsionou, D.; Tsipolitis, G.; Tsiskaridze, V.; Tskhadadze, E. G.; Tsukerman, I. I.; Tsulaia, V.; Tsung, J.-W.; Tsuno, S.; Tsybychev, D.; Tua, A.; Tuggle, J. M.; Turala, M.; Turecek, D.; Turk Cakir, I.; Turlay, E.; Turra, R.; Tuts, P. M.; Tykhonov, A.; Tylmad, M.; Tyndel, M.; Typaldos, D.; Tyrvainen, H.; Tzanakos, G.; Uchida, K.; Ueda, I.; Ueno, R.; Ugland, M.; Uhlenbrock, M.; Uhrmacher, M.; Ukegawa, F.; Unal, G.; Underwood, D. G.; Undrus, A.; Unel, G.; Unno, Y.; Urbaniec, D.; Urkovsky, E.; Urrejola, P.; Usai, G.; Uslenghi, M.; Vacavant, L.; Vacek, V.; Vachon, B.; Vahsen, S.; Valderanis, C.; Valenta, J.; Valente, P.; Valentinetti, S.; Valkar, S.; Valladolid Gallego, E.; Vallecorsa, S.; Valls Ferrer, J. A.; van der Graaf, H.; van der Kraaij, E.; van der Leeuw, R.; van der Poel, E.; van der Ster, D.; van Eijk, B.; van Eldik, N.; van Gemmeren, P.; van Kesteren, Z.; van Vulpen, I.; Vandelli, W.; Vandoni, G.; Vaniachine, A.; Vankov, P.; Vannucci, F.; Varela Rodriguez, F.; Vari, R.; Varnes, E. W.; Varouchas, D.; Vartapetian, A.; Varvell, K. E.; Vassilakopoulos, V. I.; Vazeille, F.; Vegni, G.; Veillet, J. J.; Vellidis, C.; Veloso, F.; Veness, R.; Veneziano, S.; Ventura, A.; Ventura, D.; Venturi, M.; Venturi, N.; Vercesi, V.; Verducci, M.; Verkerke, W.; Vermeulen, J. C.; Vest, A.; Vetterli, M. C.; Vichou, I.; Vickey, T.; Viehhauser, G. H. A.; Viel, S.; Villa, M.; Villaplana Perez, M.; Vilucchi, E.; Vincter, M. G.; Vinek, E.; Vinogradov, V. B.; Virchaux, M.; Viret, S.; Virzi, J.; Vitale, A.; Vitells, O.; Viti, M.; Vivarelli, I.; Vives Vaque, F.; Vlachos, S.; Vlasak, M.; Vlasov, N.; Vogel, A.; Vokac, P.; Volpi, G.; Volpi, M.; Volpini, G.; von der Schmitt, H.; von Loeben, J.; von Radziewski, H.; von Toerne, E.; Vorobel, V.; Vorobiev, A. P.; Vorwerk, V.; Vos, M.; Voss, R.; Voss, T. T.; Vossebeld, J. H.; Vovenko, A. S.; Vranjes, N.; Vranjes Milosavljevic, M.; Vrba, V.; Vreeswijk, M.; Vu Anh, T.; Vuillermet, R.; Vukotic, I.; Wagner, W.; Wagner, P.; Wahlen, H.; Wakabayashi, J.; Walbersloh, J.; Walch, S.; Walder, J.; Walker, R.; Walkowiak, W.; Wall, R.; Waller, P.; Wang, C.; Wang, H.; Wang, J.; Wang, J.; Wang, J. C.; Wang, R.; Wang, S. M.; Warburton, A.; Ward, C. P.; Warsinsky, M.; Watkins, P. M.; Watson, A. T.; Watson, M. F.; Watts, G.; Watts, S.; Waugh, A. T.; Waugh, B. M.; Weber, J.; Weber, M.; Weber, M. S.; Weber, P.; Weidberg, A. R.; Weigell, P.; Weingarten, J.; Weiser, C.; Wellenstein, H.; Wells, P. S.; Wen, M.; Wenaus, T.; Wendler, S.; Weng, Z.; Wengler, T.; Wenig, S.; Wermes, N.; Werner, M.; Werner, P.; Werth, M.; Wessels, M.; Whalen, K.; Wheeler-Ellis, S. J.; Whitaker, S. P.; White, A.; White, M. J.; White, S.; Whitehead, S. R.; Whiteson, D.; Whittington, D.; Wicek, F.; Wicke, D.; Wickens, F. J.; Wiedenmann, W.; Wielers, M.; Wienemann, P.; Wiglesworth, C.; Wiik, L. A. M.; Wijeratne, P. A.; Wildauer, A.; Wildt, M. A.; Wilhelm, I.; Wilkens, H. G.; Will, J. Z.; Williams, E.; Williams, H. H.; Willis, W.; Willocq, S.; Wilson, J. A.; Wilson, M. G.; Wilson, A.; Wingerter-Seez, I.; Winkelmann, S.; Winklmeier, F.; Wittgen, M.; Wolter, M. W.; Wolters, H.; Wooden, G.; Wosiek, B. K.; Wotschack, J.; Woudstra, M. J.; Wraight, K.; Wright, C.; Wrona, B.; Wu, S. L.; Wu, X.; Wu, Y.; Wulf, E.; Wunstorf, R.; Wynne, B. M.; Xaplanteris, L.; Xella, S.; Xie, S.; Xie, Y.; Xu, C.; Xu, D.; Xu, G.; Yabsley, B.; Yamada, M.; Yamamoto, A.; Yamamoto, K.; Yamamoto, S.; Yamamura, T.; Yamaoka, J.; Yamazaki, T.; Yamazaki, Y.; Yan, Z.; Yang, H.; Yang, U. K.; Yang, Y.; Yang, Y.; Yang, Z.; Yanush, S.; Yao, W.-M.; Yao, Y.; Yasu, Y.; Ybeles Smit, G. V.; Ye, J.; Ye, S.; Yilmaz, M.; Yoosoofmiya, R.; Yorita, K.; Yoshida, R.; Young, C.; Youssef, S.; Yu, D.; Yu, J.; Yu, J.; Yuan, L.; Yurkewicz, A.; Zaets, V. G.; Zaidan, R.; Zaitsev, A. M.; Zajacova, Z.; Zalite, Yo. K.; Zanello, L.; Zarzhitsky, P.; Zaytsev, A.; Zeitnitz, C.; Zeller, M.; Zema, P. F.; Zemla, A.; Zendler, C.; Zenin, A. V.; Zenin, O.; Ženiš, T.; Zenonos, Z.; Zenz, S.; Zerwas, D.; Zevi Della Porta, G.; Zhan, Z.; Zhang, D.; Zhang, H.; Zhang, J.; Zhang, X.; Zhang, Z.; Zhao, L.; Zhao, T.; Zhao, Z.; Zhemchugov, A.; Zheng, S.; Zhong, J.; Zhou, B.; Zhou, N.; Zhou, Y.; Zhu, C. G.; Zhu, H.; Zhu, Y.; Zhuang, X.; Zhuravlov, V.; Zieminska, D.; Zilka, B.; Zimmermann, R.; Zimmermann, S.; Zimmermann, S.; Ziolkowski, M.; Zitoun, R.; Živković, L.; Zmouchko, V. V.; Zobernig, G.; Zoccoli, A.; Zolnierowski, Y.; Zsenei, A.; Zur Nedden, M.; Zutshi, V.; Zwalinski, L.; Atlas Collaboration

2011-09-01

The inclusive J/ψ production cross-section and fraction of J/ψ mesons produced in B-hadron decays are measured in proton-proton collisions at √{s}=7 TeV with the ATLAS detector at the LHC, as a function of the transverse momentum and rapidity of the J/ψ, using 2.3 pb -1 of integrated luminosity. The cross-section is measured from a minimum p of 1 GeV to a maximum of 70 GeV and for rapidities within |y|<2.4 giving the widest reach of any measurement of J/ψ production to date. The differential production cross-sections of prompt and non-prompt J/ψ are separately determined and are compared to Colour Singlet NNLO, Colour Evaporation Model, and FONLL predictions.

Detection of singlet oxygen that uses fluorescence probe APF

NASA Astrophysics Data System (ADS)

Iwamoto, Yumiko; Awazu, Kunio

2006-04-01

The non-invasive methods of treatments have been studying for the improvement of quality of life (QOL) of patients undergoing treatment. A photodynamic therapy (PDT) is one of the non-invasive treatments. PDT is the method of treatment using interactions of a laser and a photosensitizer. PDT has few risks for patients. Furthermore, PDT enables function preservation of a disease part. PDT has been used for early cancer till now, but in late years it is applied for age-related macular degeneration (AMD). AMD is one of the causes of vision loss in older people. However, PDT for AMD does not produce the best improvement in visual acuity. The skin photosensivity by an absorption characteristic of a photosensitizer is avoided. We examined new PDT using combination of an ultra-short pulsed laser and indocyanine green (ICG).

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

PubMed

Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco B C; Hase, William L

2018-05-31

The reaction of 3 CH 2 with 3 O 2 is of fundamental importance in combustion, and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K, and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH 2 OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H 2 CO + O( 3 P), while the singlet surface leads to eight product channels with their relative importance as CO + H 2 O > CO + OH + H ∼ H 2 CO + O( 1 D) > HCO + OH ∼ CO 2 + H 2 ∼ CO + H 2 + O( 1 D) > CO 2 + H + H > HCO + O( 1 D) + H. The reaction on the singlet PES is barrierless, consistent with experiment, and the total rate constant on the singlet surface is (0.93 ± 0.22) × 10 -12 cm 3 molecule -1 s -1 in comparison to the recommended experimental rate constant of 3.3 × 10 -12 cm 3 molecule -1 s -1 . The simulation product yields for the singlet PES are compared with experiment, and the most significant differences are for H, CO 2 , and H 2 O. The reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address (1) the barrier on the triplet PES for 3 CH 2 + 3 O 2 → 3 CH 2 OO, (2) the temperature dependence of the 3 CH 2 + 3 O 2 reaction rate constant and product branching ratios, and (3) the possible non-RRKM dynamics of the 1 CH 2 OO Criegee intermediate.

Time dependence of triplet-singlet excitation transfer from compact poly rA to bound dye at 77 K.

PubMed Central

Pearlstein, R M; Van Nostrand, F; Nairn, J A

1979-01-01

The nonexponential phosphorescence decay of a highly folded form of poly-riboadenylic acid (poly rA) with noncovalently bound dye is explained by a novel application of a well-known theory of electronic excitation transfer based on the Förster mechanism. This theory, originally used to describe singlet-singlet energy transfer from donor molecules to an acceptor in a solution, is here applied to the transfer of triplet excitation from the adenine (in poly rA) to the singlet manifold of either of the bound dyes, ethidium bromide or proflavine. New experimental data are presented that allow straight-forward theoretical interpretation. These data fit the form predicted by the theory, U(t) exp(-Bt1/2), where U(t) is the decay of the poly rA phosphorescence in the absence of dye, for a range of relative concentrations of either dye. The self-consistency of these theoretical fits is demonstrated by the proportionality of B to the square root of the Förster triplet-singlet overlap integrals for transfer from poly rA to each of the dyes, as demanded by the theory. From these self-consistent values of B, the theory enables one to deduce the mean packing density of nucleotides in this folded poly rA, which we estimate to be approximately 1 nm-3. We conclude that some variations of the method described here may be useful for deducing packing densities of nucleotides in other compact nucleic acid structures. PMID:262411

Crosstalk error correction through dynamical decoupling of single-qubit gates in capacitively coupled singlet-triplet semiconductor spin qubits

NASA Astrophysics Data System (ADS)

Buterakos, Donovan; Throckmorton, Robert E.; Das Sarma, S.

2018-01-01

In addition to magnetic field and electric charge noise adversely affecting spin-qubit operations, performing single-qubit gates on one of multiple coupled singlet-triplet qubits presents a new challenge: crosstalk, which is inevitable (and must be minimized) in any multiqubit quantum computing architecture. We develop a set of dynamically corrected pulse sequences that are designed to cancel the effects of both types of noise (i.e., field and charge) as well as crosstalk to leading order, and provide parameters for these corrected sequences for all 24 of the single-qubit Clifford gates. We then provide an estimate of the error as a function of the noise and capacitive coupling to compare the fidelity of our corrected gates to their uncorrected versions. Dynamical error correction protocols presented in this work are important for the next generation of singlet-triplet qubit devices where coupling among many qubits will become relevant.

Mechanistic investigations of CO-photoextrusion and oxidative addition reactions of early transition-metal carbonyls: (η(5)-C5H5)M(CO)4 (M = V, Nb, Ta).

PubMed

Su, Shih-Hao; Su, Ming-Der

2016-06-28

The mechanisms for the photochemical Si-H bond activation reaction are studied theoretically using a model system of the group 5 organometallic compounds, η(5)-CpM(CO)4 (M = V, Nb, and Ta), with the M06-2X method and the Def2-SVPD basis set. Three types of reaction pathways that lead to final insertion products are identified. The structures of the intersystem crossings, which play a central role in these photo-activation reactions, are determined. The intermediates and transitional structures in either the singlet or triplet states are also calculated to provide a mechanistic explanation of the reaction pathways. All of the potential energy surfaces for the group 5 η(5)-CpM(CO)4 complexes are quite similar. In particular, the theoretical evidence suggests that after irradiation using light, η(5)-CpM(CO)4 quickly loses one CO ligand to yield two tricarbonyls, in either the singlet or the triplet states. The triplet tricarbonyl 16-electron intermediates, ([η(5)-CpM(CO)3](3)), play a key role in the formation of the final oxidative addition product, η(5)-CpM(CO)3(H)(SiMe3). However, the singlet counterparts, ([η(5)-CpM(CO)3](1)), play no role in the formation of the final product molecule, but their singlet metal centers interact weakly with solvent molecules ((Me3)SiH) to produce alkyl-solvated organometallic complexes, which are observable experimentally. This theoretical evidence is in accordance with the available experimental observations.

Virus Capsids as Targeted Nanoscale Delivery Vessels of Photoactive Compounds for Site-Specific Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Cohen, Brian A.

The research presented in this work details the use of a viral capsid as an addressable delivery vessel of photoactive compounds for use in photodynamic therapy. Photodynamic therapy is a treatment that involves the interaction of light with a photosensitizing molecule to create singlet oxygen, a reactive oxygen species. Overproduction of singlet oxygen in cells can cause oxidative damage leading to cytotoxicity and eventually cell death. Challenges with the current generation of FDA-approved photosensitizers for photodynamic therapy primarily stem from their lack of tissue specificity. This work describes the packaging of photoactive cationic porphyrins inside the MS2 bacteriophage capsid, followed by external modification of the capsid with cancer cell-targeting G-quadruplex DNA aptamers to generate a tumor-specific photosensitizing agent. First, a cationic porphyrin is loaded into the capsids via nucleotide-driven packaging, a process that involves charge interaction between the porphyrin and the RNA inside the capsid. Results show that over 250 porphyrin molecules associate with the RNA within each MS2 capsid. Removal of RNA from the capsid severely inhibits the packaging of the cationic porphyrins. Porphyrin-virus constructs were then shown to photogenerate singlet oxygen, and cytotoxicity in non-targeted photodynamic treatment experiments. Next, each porphyrin-loaded capsid is externally modified with approximately 60 targeting DNA aptamers by employing a heterobifunctional crosslinking agent. The targeting aptamer is known to bind the protein nucleolin, a ubiquitous protein that is overexpressed on the cell surface by many cancer cell types. MCF-7 human breast carcinoma cells and MCF-10A human mammary epithelial cells were selected as an in vitro model for breast cancer and normal tissue, respectively. Fluorescently tagged virus-aptamer constructs are shown to selectively target MCF-7 cells versus MCF-10A cells. Finally, results are shown in which porphyrin-virus-aptamer constructs selectively target and kill cancer cells versus non-cancer cells. Specifically, the results show that MS2 is a viable candidate as an addressable nanodelivery vessel of photoactive compounds, and the implications are that the nucleotide-driven packaging approach for modifying MS2 can be used to impart new functionalities for a host of diagnostic or therapeutic applications.

Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

PubMed

Broch, K; Dieterle, J; Branchi, F; Hestand, N J; Olivier, Y; Tamura, H; Cruz, C; Nichols, V M; Hinderhofer, A; Beljonne, D; Spano, F C; Cerullo, G; Bardeen, C J; Schreiber, F

2018-03-05

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

An approach to functionally relevant clustering of the protein universe: Active site profile-based clustering of protein structures and sequences.

PubMed

Knutson, Stacy T; Westwood, Brian M; Leuthaeuser, Janelle B; Turner, Brandon E; Nguyendac, Don; Shea, Gabrielle; Kumar, Kiran; Hayden, Julia D; Harper, Angela F; Brown, Shoshana D; Morris, John H; Ferrin, Thomas E; Babbitt, Patricia C; Fetrow, Jacquelyn S

2017-04-01

Protein function identification remains a significant problem. Solving this problem at the molecular functional level would allow mechanistic determinant identification-amino acids that distinguish details between functional families within a superfamily. Active site profiling was developed to identify mechanistic determinants. DASP and DASP2 were developed as tools to search sequence databases using active site profiling. Here, TuLIP (Two-Level Iterative clustering Process) is introduced as an iterative, divisive clustering process that utilizes active site profiling to separate structurally characterized superfamily members into functionally relevant clusters. Underlying TuLIP is the observation that functionally relevant families (curated by Structure-Function Linkage Database, SFLD) self-identify in DASP2 searches; clusters containing multiple functional families do not. Each TuLIP iteration produces candidate clusters, each evaluated to determine if it self-identifies using DASP2. If so, it is deemed a functionally relevant group. Divisive clustering continues until each structure is either a functionally relevant group member or a singlet. TuLIP is validated on enolase and glutathione transferase structures, superfamilies well-curated by SFLD. Correlation is strong; small numbers of structures prevent statistically significant analysis. TuLIP-identified enolase clusters are used in DASP2 GenBank searches to identify sequences sharing functional site features. Analysis shows a true positive rate of 96%, false negative rate of 4%, and maximum false positive rate of 4%. F-measure and performance analysis on the enolase search results and comparison to GEMMA and SCI-PHY demonstrate that TuLIP avoids the over-division problem of these methods. Mechanistic determinants for enolase families are evaluated and shown to correlate well with literature results. © 2017 The Authors Protein Science published by Wiley Periodicals, Inc. on behalf of The Protein Society.

The origin of the two-electron/four-centers C--C bond in pi-TCNE(2)2- dimers: electrostatic or dispersion?

PubMed

García-Yoldi, Iñigo; Mota, Fernando; Novoa, Juan J

2007-01-15

The structure and stability of the pi-TCNE(2)2- dimers in K2TCNE2 aggregates is revisited trying to find if the origin of their two-electron/four-centers C--C bond are the electrostatic K+-TCNE- interactions or the dispersion interactions between the anions. The study is done at the HF, B3LYP, CASSCF (2,2), and MCQDPT/CASSCF (2,2) levels using the 6-31+G(d) basis set. Our results show that the only minima of this aggregate that preserves the pi-TCNE(2)2- structure has the two K+ atoms placed in equatorial positions in between the two TCNE- planes. When the K+ atoms are placed along the D2h axis of the anions the structure is not a minimum. The main energetic component responsible for the stability of these aggregates comes from the cation-anion interactions. However, a proper accounting of the dispersion component (as done in the MCQDPT/CASSCF (2,2) calculations) is needed to make the closed-shell singlet more stable than the open-shell singlet. Thus, the bond results from the combination of the electrostatic and dispersion components, being the first the dominant one. The optimum geometry of the closed-shell singlet is very similar to the experimental one found in crystals. Copyright (c) 2006 Wiley Periodicals, Inc.

Charge exchange cross sections in slow collisions of Si3+ with Hydrogen atom

NASA Astrophysics Data System (ADS)

Joseph, Dwayne; Quashie, Edwin; Saha, Bidhan

2011-05-01

In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. Work supported by NSF CREST project (grant #0630370).

Laser desorption of explosives as a way to create an effective non-contact sampling device

NASA Astrophysics Data System (ADS)

Akmalov, Artem E.; Chistyakov, Alexander A.; Kotkovskii, Gennadii E.

2015-10-01

Comparison of desorption effectiveness of Nd3+:YAG nanosecond laser sources (λ=266, 354, 532 nm) has been carried out to investigate a possibility of creating a non-contact sampling device for detectors of explosives based on principles of ion mobility spectrometry (IMS) and field asymmetric ion mobility spectrometry (FAIMS). The results of mass spectrometric study of laser desorption of nitroamine, nitrate ester and nitroaromatic compounds from a quartz substrate are presented. It is shown that irradiation of adsorbed layers of studied samples by a single pulse of non-resonant laser radiation (λ=532 nm) leads to efficient desorption at laser intensity 107 W/cm2 and above. Excitation of the first singlet state of nitro compounds by resonant radiation (λ=354 nm) provides heating of adsorbed layers and thermal desorption. A strongly non-equilibrium (non-thermal) dissociation process is developed when the second singlet state of nitroaromatic molecules is excited by radiation at λ=266 nm, along with thermal desorption. It is shown that Nd3+: YAG laser with wavelength λ=266 nm, pulse duration 5-10 ns, intensity 107-109 W/cm2 is the most effective source for creation a non-contact sampling device based on desorption of explosives from surfaces.

Single Cell Responses to Spatially-Controlled Photosensitized Production of Extracellular Singlet Oxygen

PubMed Central

Pedersen, Brian Wett; Sinks, Louise E.; Breitenbach, Thomas; Schack, Nickolass B.; Vinogradov, Sergei A.; Ogilby, Peter R.

2011-01-01

The response of individual HeLa cells to extracellularly produced singlet oxygen was examined. The spatial domain of singlet oxygen production was controlled using the combination of a membrane-impermeable Pd porphyrin-dendrimer, which served as a photosensitizer, and a focused laser, which served to localize the sensitized production of singlet oxygen. Cells in close proximity to the domain of singlet oxygen production showed morphological changes commonly associated with necrotic cell death. The elapsed post-irradiation “waiting period” before necrosis became apparent depended on (a) the distance between the cell membrane and the domain irradiated, (b) the incident laser fluence and, as such, the initial concentration of singlet oxygen produced, and (c) the lifetime of singlet oxygen. The data imply that singlet oxygen plays a key role in this process of light-induced cell death. The approach of using extracellularly-generated singlet oxygen to induce cell death can provide a solution to a problem that often limits mechanistic studies of intracellularly photosensitized cell death: it can be difficult to quantify the effective light dose, and hence singlet oxygen concentration, when using an intracellular photosensitizer. PMID:21668871

A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene.

PubMed

Gritsan, N P; Gudmundsdóttir, A D; Tigelaar, D; Zhu, Z; Karney, W L; Hadad, C M; Platz, M S

2001-03-07

Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet nitrenes were detected by transient absorption spectroscopy, and their spectra are characterized by sharp absorption bands with maxima in the range of 300-365 nm. The kinetics of their decay were analyzed as a function of temperature to yield observed decay rate constants, k(OBS). The observed rate constant in inert solvents is the sum of k(R) + k(ISC) where k(R) is the absolute rate constant of rearrangement of singlet nitrene to an azirine and k(ISC) is the absolute rate constant of nitrene intersystem crossing (ISC). Values of k(R) and k(ISC) were deduced after assuming that k(ISC) is independent of temperature. Barriers to cyclization of 4-fluoro-, 3,5-difluoro-, 2-fluoro-, 2,6-difluoro-, and 2,3,4,5,6-pentafluorophenylnitrene in inert solvents are 5.3 +/- 0.3, 5.5 +/- 0.3, 6.7 +/- 0.3, 8.0 +/- 1.5, and 8.8 +/- 0.4 kcal/mol, respectively. The barrier to cyclization of parent singlet phenylnitrene is 5.6 +/- 0.3 kcal/mol. All of these values are in good quantitative agreement with CASPT2 calculations of the relative barrier heights for the conversion of fluoro-substituted singlet aryl nitrenes to benzazirines (Karney, W. L. and Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347). A single ortho-fluorine substituent exerts a small but significant bystander effect on remote cyclization that is not steric in origin. The influence of two ortho-fluorine substituents on the cyclization is pronounced. In the case of the singlet 2-fluorophenylnitrene system, evidence is presented that the benzazirine is an intermediate and that the corresponding singlet nitrene and benzazirine interconvert. Ab initio calculations at different levels of theory on a series of benzazirines, their isomeric ketenimines, and the transition states converting the benzazirines to ketenimines were performed. The computational results are in good qualitative and quantitative agreement with the experimental findings.

Optimization of hybrid blue organic light-emitting diodes based on singlet and triplet exciton diffusion length

NASA Astrophysics Data System (ADS)

Lee, Song Eun; Lee, Ho Won; Lee, Jae Woo; Hwang, Kyo Min; Park, Soo Na; Yoon, Seung Soo; Kim, Young Kwan

2015-06-01

The hybrid blue organic light-emitting diodes (HB OLEDs) with triplet harvesting (TH) structures within an emitting layer (EML) are fabricated with fluorescent and phosphorescent EMLs. The TH is to transfer triplet excitons from fluorescence to phosphorescence, where they can decay radiatively. Remarkably, the half-decay lifetime of a hybrid blue device with fluorescent and phosphorescent EML thickness of 5 and 25 nm, measured at an initial luminance of 500 cd/m2, has improved twice than that of using a conventional structure. Additionally, the blue device’s efficiency improved. We attribute this improvement to the efficient triplet excitons energy transfer and the optimized distribution of the EML which depends on singlet and triplet excitons diffusion length that occurs within each the EML.

The Contribution of Singlet Oxygen to Insulin Resistance

PubMed Central

2017-01-01

Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR), and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER) stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo)-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses. PMID:29081894

The Contribution of Singlet Oxygen to Insulin Resistance.

PubMed

Onyango, Arnold N

2017-01-01

Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR), and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER) stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo)-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses.

Hybrid spin and valley quantum computing with singlet-triplet qubits.

PubMed

Rohling, Niklas; Russ, Maximilian; Burkard, Guido

2014-10-24

The valley degree of freedom in the electronic band structure of silicon, graphene, and other materials is often considered to be an obstacle for quantum computing (QC) based on electron spins in quantum dots. Here we show that control over the valley state opens new possibilities for quantum information processing. Combining qubits encoded in the singlet-triplet subspace of spin and valley states allows for universal QC using a universal two-qubit gate directly provided by the exchange interaction. We show how spin and valley qubits can be separated in order to allow for single-qubit rotations.

Evaluation of phototoxicity of dendritic porphyrin-based phosphorescent oxygen probes: an in vitro study†

PubMed Central

Lebedev, Artem Y.; Marchi, Enrico; Yuan, Min; Esipova, Tatiana V.; Bergamini, Giacomo; Wilson, David F.

2013-01-01

Biological oxygen measurements by phosphorescence quenching make use of exogenous phosphorescent probes, which are introduced directly into the medium of interest (e.g. blood or interstitial fluid) where they serve as molecular sensors for oxygen. The byproduct of the quenching reaction is singlet oxygen, a highly reactive species capable of damaging biological tissue. Consequently, potential probe phototoxicity is a concern for biological applications. Herein, we compared the ability of polyethyleneglycol (PEG)-coated Pd tetrabenzoporphyrin (PdTBP)-based dendritic nanoprobes of three successive generations to sensitize singlet oxygen. It was found that the size of the dendrimer has practically no effect on the singlet oxygen sensitization efficiency in spite of the strong attenuation of the triplet quenching rate with an increase in the dendrimer generation. This unexpected result is due to the fact that the lifetime of the PdTBP triplet state in the absence of oxygen increases with dendritic generation, thus compensating for the concomitant decrease in the rate of quenching. Nevertheless, in spite of their ability to sensitize singlet oxygen, the phosphorescent probes were found to be non-phototoxic when compared with the commonly used photodynamic drug Photofrin in a standard cell-survival assay. The lack of phototoxicity is presumably due to the inability of PEGylated probes to associate with cell surfaces and/or penetrate cellular membranes. In contrast, conventional photosensitizers bind to cell components and act by generating singlet oxygen inside or in the immediate vicinity of cellular organelles. Therefore, PEGylated dendritic probes are safe to use for tissue oxygen measurements as long as the light doses are less than or equal to those commonly employed in photodynamic therapy. PMID:21409208

Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Yan; Guo, Zhi; Zhu, Tong

2015-09-14

Singlet fission presents an attractive solution to overcome the Shockley–Queisser limit by generating two triplet excitons from one singlet exciton. Although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. We report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. Moreover, these measurements revealmore » a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.« less

Cooperative singlet and triplet exciton transport in tetracene crystals visualized by ultrafast microscopy

NASA Astrophysics Data System (ADS)

Wan, Yan; Guo, Zhi; Zhu, Tong; Yan, Suxia; Johnson, Justin; Huang, Libai

2015-10-01

Singlet fission presents an attractive solution to overcome the Shockley-Queisser limit by generating two triplet excitons from one singlet exciton. However, although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. Here, we report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. These measurements reveal a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.

What can we learn about dispersion from the conformer surface of n-pentane?

PubMed

Martin, Jan M L

2013-04-11

In earlier work [Gruzman, D. ; Karton, A.; Martin, J. M. L. J. Phys. Chem. A 2009, 113, 11974], we showed that conformer energies in alkanes (and other systems) are highly dispersion-driven and that uncorrected DFT functionals fail badly at reproducing them, while simple empirical dispersion corrections tend to overcorrect. To gain greater insight into the nature of the phenomenon, we have mapped the torsional surface of n-pentane to 10-degree resolution at the CCSD(T)-F12 level near the basis set limit. The data obtained have been decomposed by order of perturbation theory, excitation level, and same-spin vs opposite-spin character. A large number of approximate electronic structure methods have been considered, as well as several empirical dispersion corrections. Our chief conclusions are as follows: (a) the effect of dispersion is dominated by same-spin correlation (or triplet-pair correlation, from a different perspective); (b) singlet-pair correlation is important for the surface, but qualitatively very dissimilar to the dispersion component; (c) single and double excitations beyond third order are essentially unimportant for this surface; (d) connected triple excitations do play a role but are statistically very similar to the MP2 singlet-pair correlation; (e) the form of the damping function is crucial for good performance of empirical dispersion corrections; (f) at least in the lower-energy regions, SCS-MP2 and especially MP2.5 perform very well; (g) novel spin-component scaled double hybrid functionals such as DSD-PBEP86-D2 acquit themselves very well for this problem.

Vibronic singlet and triplet steady-state interplay emissions in phenazine-based 1,2,3-triazole films

NASA Astrophysics Data System (ADS)

Costa, Bárbara B. A.; Souza, Paula D. C.; Gontijo, Rafael N.; Jardim, Guilherme A. M.; Moreira, Roberto L.; da Silva, Eufrânio N.; Cury, Luiz A.

2018-03-01

Photoluminescence and phosphorescence emissions of solid-state phenazine films were investigated in steady-state experimental conditions. Important discrepancies were observed for blended films where a host optically inert matrix was introduced to disperse the probe molecules. A vibronic spin-orbit phosphorescent emission clearly appeared, while for the films solely composed by the probe molecules, the phosphorescence broadened and presented a structureless shape, shifted to longer wavelengths. Further Arrhenius behavior analysis on the photoluminescent and phosphorescent emissions on temperature, corroborated the direct and reverse intersystem crossing interplay between singlet and triplet states. Molecular aggregation is responsible for the deterioration of non-blended triazole films phosphorescence.

Holographic monitoring of spatial distributions of singlet oxygen in water

NASA Astrophysics Data System (ADS)

Belashov, A. V.; Bel'tyukova, D. M.; Vasyutinskii, O. S.; Petrov, N. V.; Semenova, I. V.; Chupov, A. S.

2014-12-01

A method for monitoring spatial distributions of singlet oxygen in biological media has been developed. Singlet oxygen was generated using Radachlorin® photosensitizer, while thermal disturbances caused by nonradiative deactivation of singlet oxygen were detected by the holographic interferometry technique. Processing of interferograms yields temperature maps that characterize the deactivation process and show the distribution of singlet oxygen species.

Room temperature triplet state spectroscopy of organic semiconductors.

PubMed

Reineke, Sebastian; Baldo, Marc A

2014-01-21

Organic light-emitting devices and solar cells are devices that create, manipulate, and convert excited states in organic semiconductors. It is crucial to characterize these excited states, or excitons, to optimize device performance in applications like displays and solar energy harvesting. This is complicated if the excited state is a triplet because the electronic transition is 'dark' with a vanishing oscillator strength. As a consequence, triplet state spectroscopy must usually be performed at cryogenic temperatures to reduce competition from non-radiative rates. Here, we control non-radiative rates by engineering a solid-state host matrix containing the target molecule, allowing the observation of phosphorescence at room temperature and alleviating constraints of cryogenic experiments. We test these techniques on a wide range of materials with functionalities spanning multi-exciton generation (singlet exciton fission), organic light emitting device host materials, and thermally activated delayed fluorescence type emitters. Control of non-radiative modes in the matrix surrounding a target molecule may also have broader applications in light-emitting and photovoltaic devices.

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}: Structures, optical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua

Two new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} (1) and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF{sub 9} and MF{sub 6} (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F{sub 6} octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site.more » Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 µ{sub B} for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV–vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed. - Graphical abstract: Two new quaternary U(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}, were crystallized via an in situ reduction step of U(VI) to U(IV) under mild hydrothermal conditions. The compounds show complex crystal structures based on the 3-D building block of U{sub 6}F{sub 30}. Magnetic property measurements revealed that the U(IV) exhibits a nonmagnetic singlet ground state at low temperature with a spin gap. - Highlights: • Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} have been synthesized and characterized. • The U(IV) fluorides exhibit complex three-dimensional crystal structures. • The optical properties were investigated. • Magnetic susceptibility data were collected.« less

Characterization of photoactivated singlet oxygen damage in single-molecule optical trap experiments.

PubMed

Landry, Markita P; McCall, Patrick M; Qi, Zhi; Chemla, Yann R

2009-10-21

Optical traps or "tweezers" use high-power, near-infrared laser beams to manipulate and apply forces to biological systems, ranging from individual molecules to cells. Although previous studies have established that optical tweezers induce photodamage in live cells, the effects of trap irradiation have yet to be examined in vitro, at the single-molecule level. In this study, we investigate trap-induced damage in a simple system consisting of DNA molecules tethered between optically trapped polystyrene microspheres. We show that exposure to the trapping light affects the lifetime of the tethers, the efficiency with which they can be formed, and their structure. Moreover, we establish that these irreversible effects are caused by oxidative damage from singlet oxygen. This reactive state of molecular oxygen is generated locally by the optical traps in the presence of a sensitizer, which we identify as the trapped polystyrene microspheres. Trap-induced oxidative damage can be reduced greatly by working under anaerobic conditions, using additives that quench singlet oxygen, or trapping microspheres lacking the sensitizers necessary for singlet state photoexcitation. Our findings are relevant to a broad range of trap-based single-molecule experiments-the most common biological application of optical tweezers-and may guide the development of more robust experimental protocols.

Characterization of Photoactivated Singlet Oxygen Damage in Single-Molecule Optical Trap Experiments

PubMed Central

Landry, Markita P.; McCall, Patrick M.; Qi, Zhi; Chemla, Yann R.

2009-01-01

Abstract Optical traps or “tweezers” use high-power, near-infrared laser beams to manipulate and apply forces to biological systems, ranging from individual molecules to cells. Although previous studies have established that optical tweezers induce photodamage in live cells, the effects of trap irradiation have yet to be examined in vitro, at the single-molecule level. In this study, we investigate trap-induced damage in a simple system consisting of DNA molecules tethered between optically trapped polystyrene microspheres. We show that exposure to the trapping light affects the lifetime of the tethers, the efficiency with which they can be formed, and their structure. Moreover, we establish that these irreversible effects are caused by oxidative damage from singlet oxygen. This reactive state of molecular oxygen is generated locally by the optical traps in the presence of a sensitizer, which we identify as the trapped polystyrene microspheres. Trap-induced oxidative damage can be reduced greatly by working under anaerobic conditions, using additives that quench singlet oxygen, or trapping microspheres lacking the sensitizers necessary for singlet state photoexcitation. Our findings are relevant to a broad range of trap-based single-molecule experiments—the most common biological application of optical tweezers—and may guide the development of more robust experimental protocols. PMID:19843445

Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction.

PubMed

Tao, Ze; Chen, F J; Zhou, L Y; Li, Bin; Tao, Y C; Wang, J

2018-06-06

The interedge coupling is the cardinal characteristic of the narrow quantum spin Hall (QSH) insulator, and thus could bring about exotic transport phenomena. Herein, we present a theoretical investigation of the spin-resolved Andreev reflection (AR) in a QSH insulator strip touching on two neighbouring ferromagnetic insulators and one s-wave superconductor. It is demonstrated that, due to the interplay of the interedge coupling and ferromagnetic configuration, there could be not only usual local ARs leading to the spin-singlet pairing with the incident electron and Andreev-reflected hole from different spin subbands, but also novel local ARs giving rise to the spin-triplet pairing from the same spin subband. However, only the latter exists in the absence of the interedge coupling, and therefore the two pairings in turn testify the helical spin texture of the edge states. By proper tuning of the band structures of the ferromagnetic layers, under the resonance bias voltage, the usual and novel local ARs of [Formula: see text] can be all exhibited, resulting in fully spin-polarized pure spin-singlet superconductivity and pure spin-triplet superconductivity, respectively, which suggests a superconductivity switch from spin-singlet to -triplet pairing by electrical control. The results can be experimentally confirmed by the tunneling conductance and the noise power.

Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction

NASA Astrophysics Data System (ADS)

Tao, Ze; Chen, F. J.; Zhou, L. Y.; Li, Bin; Tao, Y. C.; Wang, J.

2018-06-01

The interedge coupling is the cardinal characteristic of the narrow quantum spin Hall (QSH) insulator, and thus could bring about exotic transport phenomena. Herein, we present a theoretical investigation of the spin-resolved Andreev reflection (AR) in a QSH insulator strip touching on two neighbouring ferromagnetic insulators and one s-wave superconductor. It is demonstrated that, due to the interplay of the interedge coupling and ferromagnetic configuration, there could be not only usual local ARs leading to the spin-singlet pairing with the incident electron and Andreev-reflected hole from different spin subbands, but also novel local ARs giving rise to the spin-triplet pairing from the same spin subband. However, only the latter exists in the absence of the interedge coupling, and therefore the two pairings in turn testify the helical spin texture of the edge states. By proper tuning of the band structures of the ferromagnetic layers, under the resonance bias voltage, the usual and novel local ARs of can be all exhibited, resulting in fully spin-polarized pure spin-singlet superconductivity and pure spin-triplet superconductivity, respectively, which suggests a superconductivity switch from spin-singlet to -triplet pairing by electrical control. The results can be experimentally confirmed by the tunneling conductance and the noise power.

Time dependence of triplet--singlet excitation transfer from compact poly rA to bound dye at 77 k

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearlstein, R.M.; Nostrand, F.V.; Nairn, J.A.

1979-04-01

The nonexponential phosphorescence decay of a highly folded form of polyriboadenylic acid (poly rA) with noncovalently bound dye is explained by a novel application of a well-known theory of electronic excitation transfer based on the Forster mechanism. This theory, originally used to describe singlet-singlet energy transfer from donor molecules to an acceptor in a solution, is here applied to the transfer of triplet excitation from the adenine (in poly rA) to the singlet manifold of either of the bound dyes, ethidium bromide or proflavine. New experimental data are presented that allow straight-forward theoretical interpretation. These data fit the form predictedmore » by the theory, U(t)exp(-Bt/sup 1/2/), where U(t) is the decay of the poly rA phosphorescence in the absence of dye, for a range of relative concentrations of either dye. The self-consistency of these theoretical fits is demonstrated by the proportionality of B to the square root of the Forster triplet-singlet overlap integrals for transfer from poly rA to each of the dyes, as demanded by the theory. From these self-consistent values of B, the theory enables one to deduce the mean packing density of nucleotides in this folded poly rA, which we estimate to be approx. 1 nm/sup -3/. We conclude that some variation of the method described here may be useful for deducing packing densities of nucleotides in other compact nucleic acid structures.« less

An approach to functionally relevant clustering of the protein universe: Active site profile‐based clustering of protein structures and sequences

PubMed Central

Knutson, Stacy T.; Westwood, Brian M.; Leuthaeuser, Janelle B.; Turner, Brandon E.; Nguyendac, Don; Shea, Gabrielle; Kumar, Kiran; Hayden, Julia D.; Harper, Angela F.; Brown, Shoshana D.; Morris, John H.; Ferrin, Thomas E.; Babbitt, Patricia C.

2017-01-01

Abstract Protein function identification remains a significant problem. Solving this problem at the molecular functional level would allow mechanistic determinant identification—amino acids that distinguish details between functional families within a superfamily. Active site profiling was developed to identify mechanistic determinants. DASP and DASP2 were developed as tools to search sequence databases using active site profiling. Here, TuLIP (Two‐Level Iterative clustering Process) is introduced as an iterative, divisive clustering process that utilizes active site profiling to separate structurally characterized superfamily members into functionally relevant clusters. Underlying TuLIP is the observation that functionally relevant families (curated by Structure‐Function Linkage Database, SFLD) self‐identify in DASP2 searches; clusters containing multiple functional families do not. Each TuLIP iteration produces candidate clusters, each evaluated to determine if it self‐identifies using DASP2. If so, it is deemed a functionally relevant group. Divisive clustering continues until each structure is either a functionally relevant group member or a singlet. TuLIP is validated on enolase and glutathione transferase structures, superfamilies well‐curated by SFLD. Correlation is strong; small numbers of structures prevent statistically significant analysis. TuLIP‐identified enolase clusters are used in DASP2 GenBank searches to identify sequences sharing functional site features. Analysis shows a true positive rate of 96%, false negative rate of 4%, and maximum false positive rate of 4%. F‐measure and performance analysis on the enolase search results and comparison to GEMMA and SCI‐PHY demonstrate that TuLIP avoids the over‐division problem of these methods. Mechanistic determinants for enolase families are evaluated and shown to correlate well with literature results. PMID:28054422

Quenching of porous silicon photoluminescence by molecular oxygen and dependence of this phenomenon on storing media and method of preparation of pSi photosensitizer

NASA Astrophysics Data System (ADS)

Balaguer, María; Matveeva, Eugenia

2010-10-01

The quenching of porous silicon photoluminescence (pSi PL) by molecular oxygen has been studied in different storing media in an attempt to clarify the mechanism of the energy transfer from the silicon photosensitizer to the oxygen acceptor. Luminescent materials have been prepared by two methods: electrochemical anodizing and chemical etching. Different structural forms were used: porous layers on silicon wafer and two kinds of differently prepared powder. Dry air and liquid water were employed as storing media; quenching behaviour was under observation until total degradation of quenching properties. Singlet oxygen molecules generation through energy transfer from photoluminescent pSi was the only photosensitizing mechanism observed under dry gas conditions. This PL quenching process was preferentially developed at 760 nm (1.63 eV) that corresponds to the formation of the 1Σ singlet oxygen state. Oxidation of the pSi photosensitizer was the main factor that led to its total deactivation in a time scale of few weeks. Regarding water medium, different photosensitizing behaviour was observed. In watery conditions, two preferred energy levels were found: the one detected in dry gas and another centred at approximately 2.2 eV (550 nm). Formation of reactive oxygen species (ROS) different from singlet oxygen, such as superoxide anion or superoxide radical, can be responsible for the second one. This second quenching process developed gradually after the initial contact of pSi photosensitizer with water and then degraded. The process lasted only several hours. Therefore, functionalization of the pSi photosensitizer is probably required to stabilize its PL and quenching properties in the watery physiological conditions required for biomedical applications.

Carotenoids, versatile components of oxygenic photosynthesis.

PubMed

Domonkos, Ildikó; Kis, Mihály; Gombos, Zoltán; Ughy, Bettina

2013-10-01

Carotenoids (CARs) are a group of pigments that perform several important physiological functions in all kingdoms of living organisms. CARs serve as protective agents, which are essential structural components of photosynthetic complexes and membranes, and they play an important role in the light harvesting mechanism of photosynthesizing plants and cyanobacteria. The protection against reactive oxygen species, realized by quenching of singlet oxygen and the excited states of photosensitizing molecules, as well as by the scavenging of free radicals, is one of the main biological functions of CARs. X-ray crystallographic localization of CARs revealed that they are present at functionally and structurally important sites of both the PSI and PSII reaction centers. Characterization of a CAR-less cyanobacterial mutant revealed that while the absence of CARs prevents the formation of PSII complexes, it does not abolish the assembly and function of PSI. CAR molecules assist in the formation of protein subunits of the photosynthetic complexes by gluing together their protein components. In addition to their aforementioned indispensable functions, CARs have a substantial role in the formation and maintenance of proper cellular architecture, and potentially also in the protection of the translational machinery under stress conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Metal bacteriochlorins which act as dual singlet oxygen and superoxide generators.

PubMed

Fukuzumi, Shunichi; Ohkubo, Kei; Zheng, Xiang; Chen, Yihui; Pandey, Ravindra K; Zhan, Riqiang; Kadish, Karl M

2008-03-06

A series of stable free-base, Zn(II) and Pd(II) bacteriochlorins containing a fused six- or five-member diketo- or imide ring have been synthesized as good candidates for photodynamic therapy sensitizers, and their electrochemical, photophysical, and photochemical properties were examined. Photoexcitation of the palladium bacteriochlorin affords the triplet excited state without fluorescence emission, resulting in formation of singlet oxygen with a high quantum yield due to the heavy atom effect of palladium. Electrochemical studies revealed that the zinc bacteriochlorin has the smallest HOMO-LUMO gap of the investigated compounds, and this value is significantly lower than the triplet excited-state energy of the compound in benzonitrile. Such a small HOMO-LUMO gap of the zinc bacteriochlorin enables intermolecular photoinduced electron transfer from the triplet excited state to the ground state to produce both the radical cation and the radical anion. The radical anion thus produced can transfer an electron to molecular oxygen to produce superoxide anion which was detected by electron spin resonance. The same photosensitizer can also act as an efficient singlet oxygen generator. Thus, the same zinc bacteriochlorin can function as a sensitizer with a dual role in that it produces both singlet oxygen and superoxide anion in an aprotic solvent (benzonitrile).

Cholesterol Hydroperoxide Generation, Translocation, and Reductive Turnover in Biological Systems.

PubMed

Girotti, Albert W; Korytowski, Witold

2017-12-01

Cholesterol is like other unsaturated lipids in being susceptible to peroxidative degradation upon exposure to strong oxidants like hydroxyl radical or peroxynitrite generated under conditions of oxidative stress. In the eukaryotic cell plasma membrane, where most of the cellular cholesterol resides, peroxidation leads to membrane structural and functional damage from which pathological states may arise. In low density lipoprotein, cholesterol and phospholipid peroxidation have long been associated with atherogenesis. Among the many intermediates/products of cholesterol oxidation, hydroperoxide species (ChOOHs) have a number of different fates and deserve special attention. These fates include (a) damage-enhancement via iron-catalyzed one-electron reduction, (b) damage containment via two-electron reduction, and (c) inter-membrane, inter-lipoprotein, and membrane-lipoprotein translocation, which allows dissemination of one-electron damage or off-site suppression thereof depending on antioxidant location and capacity. In addition, ChOOHs can serve as reliable and conveniently detected mechanistic reporters of free radical-mediated reactions vs. non-radical (e.g., singlet oxygen)-mediated reactions. Iron-stimulated peroxidation of cholesterol and other lipids underlies a newly discovered form of regulated cell death called ferroptosis. These and other deleterious consequences of radical-mediated lipid peroxidation will be discussed in this review.

Asymptotically Free Gauge Theories. I

DOE R&D Accomplishments Database

Wilczek, Frank; Gross, David J.

1973-07-01

Asymptotically free gauge theories of the strong interactions are constructed and analyzed. The reasons for doing this are recounted, including a review of renormalization group techniques and their application to scaling phenomena. The renormalization group equations are derived for Yang-Mills theories. The parameters that enter into the equations are calculated to lowest order and it is shown that these theories are asymptotically free. More specifically the effective coupling constant, which determines the ultraviolet behavior of the theory, vanishes for large space-like momenta. Fermions are incorporated and the construction of realistic models is discussed. We propose that the strong interactions be mediated by a "color" gauge group which commutes with SU(3)xSU(3). The problem of symmetry breaking is discussed. It appears likely that this would have a dynamical origin. It is suggested that the gauge symmetry might not be broken, and that the severe infrared singularities prevent the occurrence of non-color singlet physical states. The deep inelastic structure functions, as well as the electron position total annihilation cross section are analyzed. Scaling obtains up to calculable logarithmic corrections, and the naive lightcone or parton model results follow. The problems of incorporating scalar mesons and breaking the symmetry by the Higgs mechanism are explained in detail.

The entangled triplet pair state in acene and heteroacene materials

PubMed Central

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-01-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (∼30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg–Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency. PMID:28699637

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers

DOE PAGES

Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B.; ...

2016-05-05

Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley–Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ~2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). But, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur viamore » a direct coupling mechanism that is independent of CT states. Moreover, we show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, despite weak direct coupling.« less

Equal-Spin Andreev Reflection on Junctions of Spin-Resolved Quantum Hall Bulk State and Spin-Singlet Superconductor.

PubMed

Matsuo, Sadashige; Ueda, Kento; Baba, Shoji; Kamata, Hiroshi; Tateno, Mizuki; Shabani, Javad; Palmstrøm, Christopher J; Tarucha, Seigo

2018-02-22

The recent development of superconducting spintronics has revealed the spin-triplet superconducting proximity effect from a spin-singlet superconductor into a spin-polarized normal metal. In addition recently superconducting junctions using semiconductors are in demand for highly controlled experiments to engineer topological superconductivity. Here we report experimental observation of Andreev reflection in junctions of spin-resolved quantum Hall (QH) states in an InAs quantum well and the spin-singlet superconductor NbTi. The measured conductance indicates a sub-gap feature and two peaks on the outer side of the sub-gap feature in the QH plateau-transition regime increases. The observed structures can be explained by considering transport with Andreev reflection from two channels, one originating from equal-spin Andreev reflection intermediated by spin-flip processes and second arising from normal Andreev reflection. This result indicates the possibility to induce the superconducting proximity gap in the the QH bulk state, and the possibility for the development of superconducting spintronics in semiconductor devices.

The entangled triplet pair state in acene and heteroacene materials

NASA Astrophysics Data System (ADS)

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-07-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (~30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg-Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency.

On The Geometric Nature of ``Singlet Fission'' in Certain Crystalline Conjugated Polymers

NASA Astrophysics Data System (ADS)

Rahman, Noah

2013-03-01

In recent years, the coherent fission of low-lying singlet electronic excitations in conjugated polymers has attracted interest as a possible way to exceed the Shockley-Queisser limit in organic photovoltaics. Femtosecond spectroscopic and fluorescence measurements of such singlets and the resulting triplets in crystalline anthracene, tetracene and naphthalene reveal curious phenomena associated with certain vibrational modes, such as ultrafast propagation on a timescale inconsistent with conventional intersystem crossing, long-lived electronic coherence, and triplet magnetic anisotropy whose structure is consistent across all three materials. This conflicts with NRG and quantum chemical simulations, which posit isotropic triplets. I explain this by a dynamical Rashba spin-orbit interaction that decays as R-6. This arises from a geometric SU(2) gauge potential generated by a nuclear-motion-induced parametric near-degeneracy of the molecular electronic states. The anisotropy is shown to follow from the work of Affleck and Oshikawa on spin one-half Heisenberg chains. Possible directions for future work are discussed, especially with regard to adiabatic pumping and topological insulators.

Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material.

PubMed

Hajdu, Kata; Ur Rehman, Ateeq; Vass, Imre; Nagy, László

2017-12-26

Photosynthetic reaction center proteins (RCs) are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs). Carboxyl-and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of ¹O₂ either by physical (resonance) energy transfer or by chemical (oxidation) reaction and their efficiency showed dependence on the diffusion distance of ¹O₂.

Singlet particles as cold dark matter in a noncommutative space-time

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ettefaghi, M. M.

2009-03-15

We extend the noncommutative (NC) standard model to incorporate singlet particles as cold dark matter. In the NC space-time, the singlet particles can be coupled to the U(1) gauge field in the adjoint representation. We study the relic density of the singlet particles due to the NC induced interaction. Demanding either the singlet fermion or the singlet scalar to serve as cold dark matter and the NC induced interactions to be relevant to the dark matter production, we obtain the corresponding relations between the NC scale and the dark matter masses, which are consistent with some existing bounds.

Singlet oxygen signatures are detected independent of light or chloroplasts in response to multiple stresses.

PubMed

Mor, Avishai; Koh, Eugene; Weiner, Lev; Rosenwasser, Shilo; Sibony-Benyamini, Hadas; Fluhr, Robert

2014-05-01

The production of singlet oxygen is typically associated with inefficient dissipation of photosynthetic energy or can arise from light reactions as a result of accumulation of chlorophyll precursors as observed in fluorescent (flu)-like mutants. Such photodynamic production of singlet oxygen is thought to be involved in stress signaling and programmed cell death. Here we show that transcriptomes of multiple stresses, whether from light or dark treatments, were correlated with the transcriptome of the flu mutant. A core gene set of 118 genes, common to singlet oxygen, biotic and abiotic stresses was defined and confirmed to be activated photodynamically by the photosensitizer Rose Bengal. In addition, induction of the core gene set by abiotic and biotic selected stresses was shown to occur in the dark and in nonphotosynthetic tissue. Furthermore, when subjected to various biotic and abiotic stresses in the dark, the singlet oxygen-specific probe Singlet Oxygen Sensor Green detected rapid production of singlet oxygen in the Arabidopsis (Arabidopsis thaliana) root. Subcellular localization of Singlet Oxygen Sensor Green fluorescence showed its accumulation in mitochondria, peroxisomes, and the nucleus, suggesting several compartments as the possible origins or targets for singlet oxygen. Collectively, the results show that singlet oxygen can be produced by multiple stress pathways and can emanate from compartments other than the chloroplast in a light-independent manner. The results imply that the role of singlet oxygen in plant stress regulation and response is more ubiquitous than previously thought.

Singlet Oxygen Signatures Are Detected Independent of Light or Chloroplasts in Response to Multiple Stresses1[C][W

PubMed Central

Mor, Avishai; Koh, Eugene; Weiner, Lev; Rosenwasser, Shilo; Sibony-Benyamini, Hadas; Fluhr, Robert

2014-01-01

The production of singlet oxygen is typically associated with inefficient dissipation of photosynthetic energy or can arise from light reactions as a result of accumulation of chlorophyll precursors as observed in fluorescent (flu)-like mutants. Such photodynamic production of singlet oxygen is thought to be involved in stress signaling and programmed cell death. Here we show that transcriptomes of multiple stresses, whether from light or dark treatments, were correlated with the transcriptome of the flu mutant. A core gene set of 118 genes, common to singlet oxygen, biotic and abiotic stresses was defined and confirmed to be activated photodynamically by the photosensitizer Rose Bengal. In addition, induction of the core gene set by abiotic and biotic selected stresses was shown to occur in the dark and in nonphotosynthetic tissue. Furthermore, when subjected to various biotic and abiotic stresses in the dark, the singlet oxygen-specific probe Singlet Oxygen Sensor Green detected rapid production of singlet oxygen in the Arabidopsis (Arabidopsis thaliana) root. Subcellular localization of Singlet Oxygen Sensor Green fluorescence showed its accumulation in mitochondria, peroxisomes, and the nucleus, suggesting several compartments as the possible origins or targets for singlet oxygen. Collectively, the results show that singlet oxygen can be produced by multiple stress pathways and can emanate from compartments other than the chloroplast in a light-independent manner. The results imply that the role of singlet oxygen in plant stress regulation and response is more ubiquitous than previously thought. PMID:24599491

Short-time dynamics of 2-thiouracil in the light absorbing S{sub 2}(ππ{sup ∗}) state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Jie; Zhang, Teng-shuo; Xue, Jia-dan

2015-11-07

Ultrahigh quantum yields of intersystem crossing to the lowest triplet state T{sub 1} are observed for 2-thiouracils (2TU), which is in contrast to the natural uracils that predominantly exhibit ultrafast internal conversion to the ground state upon excitation to the singlet excited state. The intersystem crossing mechanism of 2TU has recently been investigated using second-order perturbation methods with a high-level complete-active space self-consistent field. Three competitive nonadiabatic pathways to the lowest triplet state T{sub 1} from the initially populated singlet excited state S{sub 2} were proposed. We investigate the initial decay dynamics of 2TU from the light absorbing excited statesmore » using resonance Raman spectroscopy, time-dependent wave-packet theory in the simple model, and complete-active space self-consistent field (CASSCF) and time dependent-Becke’s three-parameter exchange and correlation functional with the Lee-Yang-Parr correlation functional (TD-B3LYP) calculations. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were compared with the CASSCF(16,11) predicted key nonadiabatic decay routes. Our results indicate that the predominant decay pathway initiated at the Franck-Condon region is toward the S{sub 2}/S{sub 1} conical intersection point and S{sub 2}T{sub 3} intersystem crossing point, but not toward the S{sub 2}T{sub 2} intersystem crossing point.« less

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

PubMed Central

Ho, Junming; Kish, Elizabeth; Méndez-Hernández, Dalvin D.; WongCarter, Katherine; Pillai, Smitha; Kodis, Gerdenis; Niklas, Jens; Poluektov, Oleg G.; Gust, Devens; Moore, Thomas A.; Moore, Ana L.; Batista, Victor S.

2017-01-01

In photosynthetic organisms, protection against photooxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll-to-carotenoid triplet–triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, whereas it is ultrafast in the oxygen-rich chloroplasts of oxygen-evolving photosynthetic organisms. To better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomeric carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET, including a resonance Raman-based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by density functional theory (DFT) calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light-harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). Both DFT and electron paramagnetic resonance (EPR) analyses further indicate that, upon T-TET, the triplet wave function is localized on the carotenoid in both dyads. PMID:28652359

Color-suppression of non-planar diagrams in bosonic bound states

NASA Astrophysics Data System (ADS)

Alvarenga Nogueira, J. H.; Ji, Chueng-Ryong; Ydrefors, E.; Frederico, T.

2018-02-01

We study the suppression of non-planar diagrams in a scalar QCD model of a meson system in 3 + 1 space-time dimensions due to the inclusion of the color degrees of freedom. As a prototype of the color-singlet meson, we consider a flavor-nonsinglet system consisting of a scalar-quark and a scalar-antiquark with equal masses exchanging a scalar-gluon of a different mass, which is investigated within the framework of the homogeneous Bethe-Salpeter equation. The equation is solved by using the Nakanishi representation for the manifestly covariant bound-state amplitude and its light-front projection. The resulting non-singular integral equation is solved numerically. The damping of the impact of the cross-ladder kernel on the binding energies are studied in detail. The color-suppression of the cross-ladder effects on the light-front wave function and the elastic electromagnetic form factor are also discussed. As our results show, the suppression appears significantly large for Nc = 3, which supports the use of rainbow-ladder truncations in practical non-perturbative calculations within QCD.

An Exponential Regulator for Rapidity Divergences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Ye; Neill, Duff; Zhu, Hua Xing

2016-04-01

Finding an efficient and compelling regularization of soft and collinear degrees of freedom at the same invariant mass scale, but separated in rapidity is a persistent problem in high-energy factorization. In the course of a calculation, one encounters divergences unregulated by dimensional regularization, often called rapidity divergences. Once regulated, a general framework exists for their renormalization, the rapidity renormalization group (RRG), leading to fully resummed calculations of transverse momentum (to the jet axis) sensitive quantities. We examine how this regularization can be implemented via a multi-differential factorization of the soft-collinear phase-space, leading to an (in principle) alternative non-perturbative regularization ofmore » rapidity divergences. As an example, we examine the fully-differential factorization of a color singlet's momentum spectrum in a hadron-hadron collision at threshold. We show how this factorization acts as a mother theory to both traditional threshold and transverse momentum resummation, recovering the classical results for both resummations. Examining the refactorization of the transverse momentum beam functions in the threshold region, we show that one can directly calculate the rapidity renormalized function, while shedding light on the structure of joint resummation. Finally, we show how using modern bootstrap techniques, the transverse momentum spectrum is determined by an expansion about the threshold factorization, leading to a viable higher loop scheme for calculating the relevant anomalous dimensions for the transverse momentum spectrum.« less

Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.

PubMed

Freeman, David M E; Musser, Andrew J; Frost, Jarvist M; Stern, Hannah L; Forster, Alexander K; Fallon, Kealan J; Rapidis, Alexandros G; Cacialli, Franco; McCulloch, Iain; Clarke, Tracey M; Friend, Richard H; Bronstein, Hugo

2017-08-16

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Planar pyrochlore: A strong-coupling analysis

NASA Astrophysics Data System (ADS)

Brenig, Wolfram; Honecker, Andreas

2002-04-01

Recent investigations of the two-dimensional spin-1/2 checkerboard lattice favor a valence bond crystal with long-range quadrumer order [J.-B. Fouet, M. Mambrini, P. Sindzingre, and C. Lhuillier, cond-mat/0108070 (unpublished)]. Starting from the limit of isolated quadrumers, we perform a complementary analysis of the evolution of the spectrum as a function of the interquadrumer coupling j using both exact diagonalization (ED) and series expansion (SE) by continuous unitary transformation. We compute (i) the ground-state energy, (ii) the elementary triplet excitations, and (iii) singlet excitations on finite systems and find very good agreement between SE and ED. In the thermodynamic limit we find a ground-state energy substantially lower than that documented in the literature. The elementary triplet excitation is shown to be gapped and almost dispersionless, whereas the singlet sector contains strongly dispersive modes. Evidence is presented for the low energy singlet excitations in the spin gap in the vicinity of j=1 to result from a large downward renormalization of local high-energy states.

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering.

PubMed

Lukman, Steven; Chen, Kai; Hodgkiss, Justin M; Turban, David H P; Hine, Nicholas D M; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C; Musser, Andrew J

2016-12-07

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering

PubMed Central

Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.; Turban, David H. P.; Hine, Nicholas D. M.; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C.; Musser, Andrew J.

2016-01-01

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics. PMID:27924819

Rotationally resolved electronic spectroscopy study of the conformational space of 3-methoxyphenol

NASA Astrophysics Data System (ADS)

Wilke, Martin; Schneider, Michael; Wilke, Josefin; Ruiz-Santoyo, José Arturo; Campos-Amador, Jorge J.; González-Medina, M. Elena; Álvarez-Valtierra, Leonardo; Schmitt, Michael

2017-07-01

Conformational preferences are determined by (de-)stabilization effects like intramolecular hydrogen bonds or steric hindrance of adjacent substituents and thus, influence the stability and reactivity of the conformers. In the present contribution, we investigate the conformational landscape of 3-methoxyphenol using a combination of high resolution electronic spectroscopy and ab initio calculations. Three of the four possible conformational isomers were characterized in their electronic ground and lowest excited singlet states on the basis of their rotational constants and other molecular parameters. The absence of one conformer in molecular beam studies can be explained by its non-planar structure in the excited state, which leads to a vanishingly small Franck-Condon factor of the respective origin excitation.

Minimizing Higgs potentials via numerical polynomial homotopy continuation

NASA Astrophysics Data System (ADS)

Maniatis, M.; Mehta, D.

2012-08-01

The study of models with extended Higgs sectors requires to minimize the corresponding Higgs potentials, which is in general very difficult. Here, we apply a recently developed method, called numerical polynomial homotopy continuation (NPHC), which guarantees to find all the stationary points of the Higgs potentials with polynomial-like non-linearity. The detection of all stationary points reveals the structure of the potential with maxima, metastable minima, saddle points besides the global minimum. We apply the NPHC method to the most general Higgs potential having two complex Higgs-boson doublets and up to five real Higgs-boson singlets. Moreover the method is applicable to even more involved potentials. Hence the NPHC method allows to go far beyond the limits of the Gröbner basis approach.

Pseudosmooth tribrid inflation

NASA Astrophysics Data System (ADS)

Antusch, Stefan; Nolde, David; Rehman, Mansoor Ur

2012-08-01

We explore a new class of supersymmetric models of inflation where the inflaton is realised as a combination of a Higgs field and (gauge non-singlet) matter fields, using a ``tribrid'' structure of the superpotential. Inflation is associated with a phase transition around GUT scale energies. The inflationary trajectory already preselects the later vacuum after inflation, which has the advantage of automatically avoiding the production of dangerous topological defects at the end of inflation. While at first sight the models look similar to smooth inflation, they feature a waterfall and are therefore only pseudosmooth. The new class of models offers novel possibilities for realising inflation in close contact with particle physics, for instance with supersymmetric GUTs or with supersymmetric flavour models based on family symmetries.

Singlet oxygen detection in biological systems: Uses and limitations.

PubMed

Koh, Eugene; Fluhr, Robert

2016-07-02

The study of singlet oxygen in biological systems is challenging in many ways. Singlet oxygen is a relatively unstable ephemeral molecule, and its properties make it highly reactive with many biomolecules, making it difficult to quantify accurately. Several methods have been developed to study this elusive molecule, but most studies thus far have focused on those conditions that produce relatively large amounts of singlet oxygen. However, the need for more sensitive methods is required as one begins to explore the levels of singlet oxygen required in signaling and regulatory processes. Here we discuss the various methods used in the study of singlet oxygen, and outline their uses and limitations.

Singlet oxygen production in Chlamydomonas reinhardtii under heat stress.

PubMed

Prasad, Ankush; Ferretti, Ursula; Sedlářová, Michaela; Pospíšil, Pavel

2016-02-01

In the current study, singlet oxygen formation by lipid peroxidation induced by heat stress (40 °C) was studied in vivo in unicellular green alga Chlamydomonas reinhardtii. Primary and secondary oxidation products of lipid peroxidation, hydroperoxide and malondialdehyde, were generated under heat stress as detected using swallow-tailed perylene derivative fluorescence monitored by confocal laser scanning microscopy and high performance liquid chromatography, respectively. Lipid peroxidation was initiated by enzymatic reaction as inhibition of lipoxygenase by catechol and caffeic acid prevented hydroperoxide formation. Ultra-weak photon emission showed formation of electronically excited species such as triplet excited carbonyl, which, upon transfer of excitation energy, leads to the formation of either singlet excited chlorophyll or singlet oxygen. Alternatively, singlet oxygen is formed by direct decomposition of hydroperoxide via Russell mechanisms. Formation of singlet oxygen was evidenced by the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl detected by electron paramagnetic resonance spin-trapping spectroscopy and the imaging of green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. Suppression of singlet oxygen formation by lipoxygenase inhibitors indicates that singlet oxygen may be formed via enzymatic lipid peroxidation initiated by lipoxygenase.

Pressure effect on the energy structure and superexchange interaction in undoped orthorhombic La2CuO4

NASA Astrophysics Data System (ADS)

Gavrichkov, Vladimir A.; Pchelkina, Zlata V.; Nekrasov, Igor A.; Ovchinnikov, Sergey G.

2016-09-01

We studied the pressure dependences of the electronic structure and superexchange interaction J(P) = JA - JB (where JA and JB are antiferromagnetic (AFM) and ferromagnetic (FM) contributions) in antiferromagnetic La214 under hydrostatic, uniaxial (along c-axial) 3% compressions and 1% in-plane compressions by the local density approximation with generalized tight-binding method (LDA + GTB cell approach). The changes in J(P) correlated with the experimentally known TC(P) dependence are in accordance with the relation dTC/dP = (∂TC/∂J)(∂J/∂P), where ∂TC/∂J ˜ 0.1. The in-plane pressure more effectively stabilizes the ground singlet two-hole state A1 than the simple hydrostatic pressure, its effect on J and TC is the largest. Within the same cell approach together with the superexchange interaction J(P), the valence band structure was calculated. Its changes with pressure clearly reproduce the k-distribution of the singlet and triplet quasi-particles over the Brillouin zone (BZ).

Static holes in the geometrically frustrated bow-tie ladder

NASA Astrophysics Data System (ADS)

Martins, George B.; Brenig, Wolfram

2008-10-01

We investigate the doping of a geometrically frustrated spin ladder with static holes by a complementary approach using exact diagonalization and quantum dimers. Results for thermodynamic properties, the singlet density of states, the hole-binding energy and the spin correlations will be presented. For the undoped systems the ground state is non-degenerate, with translationally invariant nearest-neighbor spin correlations. For the doped case, we find that static holes polarize their vicinity through a localization of singlets, reducing the frustration. This polarization induces short range repulsive forces between two holes and an oscillatory behavior of the long range two-hole energy. For most quantities investigated, we find very good agreement between the quantum dimer approach and the results from exact diagonalization.

Phenomenological model of photoluminescence degradation and photoinduced defect formation in silicon nanocrystal ensembles under singlet oxygen generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gongalsky, Maxim B., E-mail: mgongalsky@gmail.com; Timoshenko, Victor Yu.

2014-12-28

We propose a phenomenological model to explain photoluminescence degradation of silicon nanocrystals under singlet oxygen generation in gaseous and liquid systems. The model considers coupled rate equations, which take into account the exciton radiative recombination in silicon nanocrystals, photosensitization of singlet oxygen generation, defect formation on the surface of silicon nanocrystals as well as quenching processes for both excitons and singlet oxygen molecules. The model describes well the experimentally observed power law dependences of the photoluminescence intensity, singlet oxygen concentration, and lifetime versus photoexcitation time. The defect concentration in silicon nanocrystals increases by power law with a fractional exponent, whichmore » depends on the singlet oxygen concentration and ambient conditions. The obtained results are discussed in a view of optimization of the photosensitized singlet oxygen generation for biomedical applications.« less

Identification of singlet oxygen photosensitizes in lambs drinking water in an alveld risk area in West Norway.

PubMed

Tønnesen, Hanne Hjorth; Mysterud, Ivar; Karlsen, Jan; Skulberg, Olav M; Laane, Carl M M; Schumacher, Trond

2013-02-05

Alveld is a hepatogenous photosensitivity disorder in lambs. Although alveld has been known in Norway for more than 100years, there are still questions related to the cause of the disease. Phytoporphyrin has long been incriminated as the photosensitizer in hepatogenous photosensitivity diseases but previous findings suggest that the photosensitizing mechanism in alveld is more complex, possibly involving other co-factors. The current work investigates the presence of non-hepatogenous photosensitizers originating in lamb's drinking water from various sources. In addition samples of two of the predominent cyanobacteria found in a representative biofilm (i.e. aggregates of microbes) were identified and isolated in axenic (i.e. pure) cultures. Information from the absorption-, fluorescence emission-, and -excitation spectra and the action spectrum for the formation of singlet oxygen was combined in order to identify the chromophores responsible for the formation of singlet oxygen, e.g. phycocyanins from the cyanobacteria. The highest level of singlet oxygen formation was detected in lotic (i.e. flowing) water in the period consistent with the outbreak of the alveld disease in the area. Meteorological data indicate a warm and wet May with a high radiation exposure leading up to a colder and wet June with an even higher solar irradiance. The seasonal variation in the amount of photosensitizers in lamb's drinking water combined meteorological data can be important to predict the outbreak of alveld. Copyright © 2012 Elsevier B.V. All rights reserved.

Cytochrome c-promoted cardiolipin oxidation generates singlet molecular oxygen.

PubMed

Miyamoto, Sayuri; Nantes, Iseli L; Faria, Priscila A; Cunha, Daniela; Ronsein, Graziella E; Medeiros, Marisa H G; Di Mascio, Paolo

2012-10-01

The interaction of cytochrome c (cyt c) with cardiolipin (CL) induces protein conformational changes that favor peroxidase activity. This process has been correlated with CL oxidation and the induction of cell death. Here we report evidence demonstrating the generation of singlet molecular oxygen [O(2)((1)Δ(g))] by a cyt c-CL complex in a model membrane containing CL. The formation of singlet oxygen was directly evidenced by luminescence measurements at 1270 nm and by chemical trapping experiments. Singlet oxygen generation required cyt c-CL binding and occurred at pH values higher than 6, consistent with lipid-protein interactions involving fully deprotonated CL species and positively charged residues in the protein. Moreover, singlet oxygen formation was specifically observed for tetralinoleoyl CL species and was not observed with monounsaturated and saturated CL species. Our results show that there are at least two mechanisms leading to singlet oxygen formation: one with fast kinetics involving the generation of singlet oxygen directly from CL hydroperoxide decomposition and the other involving CL oxidation. The contribution of the first mechanism was clearly evidenced by the detection of labeled singlet oxygen [(18)O(2)((1)Δ(g))] from liposomes supplemented with 18-oxygen-labeled CL hydroperoxides. However quantitative analysis showed that singlet oxygen yield from CL hydroperoxides was minor (<5%) and that most of the singlet oxygen is formed from the second mechanism. Based on these data and previous findings we propose a mechanism of singlet oxygen generation through reactions involving peroxyl radicals (Russell mechanism) and excited triplet carbonyl intermediates (energy transfer mechanism).

Blinking fluorescence of single donor-acceptor pairs: important role of "dark'' states in resonance energy transfer via singlet levels.

PubMed

Osad'ko, I S; Shchukina, A L

2012-06-01

The influence of triplet levels on Förster resonance energy transfer via singlet levels in donor-acceptor (D-A) pairs is studied. Four types of D-A pair are considered: (i) two-level donor and two-level acceptor, (ii) three-level donor and two-level acceptor, (iii) two-level donor and three-level acceptor, and (iv) three-level donor and three-level acceptor. If singlet-triplet transitions in a three-level acceptor molecule are ineffective, the energy transfer efficiency E=I_{A}/(I_{A}+I_{D}), where I_{D} and I_{A} are the average intensities of donor and acceptor fluorescence, can be described by the simple theoretical equation E(F)=FT_{D}/(1+FT_{D}). Here F is the rate of energy transfer, and T_{D} is the donor fluorescence lifetime. In accordance with the last equation, 100% of the donor electronic energy can be transferred to an acceptor molecule at FT_{D}≫1. However, if singlet-triplet transitions in a three-level acceptor molecule are effective, the energy transfer efficiency is described by another theoretical equation, E(F)=F[over ¯](F)T_{D}/[1+F[over ¯](F)T_{D}]. Here F[over ¯](F) is a function of F depending on singlet-triplet transitions in both donor and acceptor molecules. Expressions for the functions F[over ¯](F) are derived. In this case the energy transfer efficiency will be far from 100% even at FT_{D}≫1. The character of the intensity fluctuations of donor and acceptor fluorescence indicates which of the two equations for E(F) should be used to find the value of the rate F. Therefore, random time instants of photon emission in both donor and acceptor fluorescence are calculated by the Monte Carlo method for all four types of D-A pair. Theoretical expressions for start-stop correlators (waiting time distributions) in donor and acceptor fluorescence are derived. The probabilities w_{N}^{D}(t) and w_{N}^{A}(t) of finding N photons of donor and acceptor fluorescence in the time interval t are calculated for various values of the energy transfer rate F and for all four types of D-A pair. Comparison of the calculated D and A fluorescence trajectories with those measured by Weiss and co-workers proves the important role of triplet levels in energy transfer via singlet levels.

Bound H dibaryon in flavor SU(3) limit of lattice QCD.

PubMed

Inoue, Takashi; Ishii, Noriyoshi; Aoki, Sinya; Doi, Takumi; Hatsuda, Tetsuo; Ikeda, Yoichi; Murano, Keiko; Nemura, Hidekatsu; Sasaki, Kenji

2011-04-22

The flavor-singlet H dibaryon, which has strangeness -2 and baryon number 2, is studied by the approach recently developed for the baryon-baryon interactions in lattice QCD. The flavor-singlet central potential is derived from the spatial and imaginary-time dependence of the Nambu-Bethe-Salpeter wave function measured in N(f)=3 full QCD simulations with the lattice size of L≃2,3,4  fm. The potential is found to be insensitive to the volume, and it leads to a bound H dibaryon with the binding energy of 30-40 MeV for the pseudoscalar meson mass of 673-1015 MeV.

High-Fidelity Single-Shot Singlet-Triplet Readout of Precision-Placed Donors in Silicon.

PubMed

Broome, M A; Watson, T F; Keith, D; Gorman, S K; House, M G; Keizer, J G; Hile, S J; Baker, W; Simmons, M Y

2017-07-28

In this work we perform direct single-shot readout of the singlet-triplet states in exchange coupled electrons confined to precision-placed donor atoms in silicon. Our method takes advantage of the large energy splitting given by the Pauli-spin blockaded (2,0) triplet states, from which we can achieve a single-shot readout fidelity of 98.4±0.2%. We measure the triplet-minus relaxation time to be of the order 3 s at 2.5 T and observe its predicted decrease as a function of magnetic field, reaching 0.5 s at 1 T.

The road to superconducting spintronics

NASA Astrophysics Data System (ADS)

Eschrig, Matthias

Energy efficient computing has become a major challenge, with the increasing importance of large data centres across the world, which already today have a power consumption comparable to that of Spain, with steeply increasing trend. Superconducting computing is progressively becoming an alternative for large-scale applications, with the costs for cooling being largely outweighed by the gain in energy efficiency. The combination of superconductivity and spintronics - ``superspintronics'' - has the potential and flexibility to develop into such a green technology. This young field is based on the observation that new phenomena emerge at interfaces between superconducting and other, competing, phases. The past 15 years have seen a series of pivotal predictions and experimental discoveries relating to the interplay between superconductivity and ferromagnetism. The building blocks of superspintronics are equal-spin Cooper pairs, which are generated at the interface between superconducting and a ferromagnetic materials in the presence of non-collinear magnetism. Such novel, spin-polarised Cooper pairs carry spin-supercurrents in ferromagnets and thus contribute to spin-transport and spin-control. Geometric Berry phases appear during the singlet-triplet conversion process in structures with non-coplanar magnetisation, enhancing functionality of devices, and non-locality introduced by superconducting order leads to long-range effects. With the successful generation and control of equal-spin Cooper pairs the hitherto notorious incompatibility of superconductivity and ferromagnetism has been not only overcome, but turned synergistic. I will discuss these developments and their extraordinary potential. I also will present open questions posed by recent experiments and point out implications for theory. This work is supported by the Engineering and Physical Science Research Council (EPSRC Grant No. EP/J010618/1).

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents.

PubMed

Kumar, Karuppannan Senthil; Selvaraju, Chellappan; Malar, Ezekiel Joy Padma; Natarajan, Paramasivam

2012-01-12

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant lifetime observed for proflavine in different solvents is suggested to be due to the similar dipole moments of the ground and the evolved emitting singlet state of the dye from the Franck-Condon excited state.

Singlet oxygen detection in biological systems: Uses and limitations

PubMed Central

Koh, Eugene; Fluhr, Robert

2016-01-01

ABSTRACT The study of singlet oxygen in biological systems is challenging in many ways. Singlet oxygen is a relatively unstable ephemeral molecule, and its properties make it highly reactive with many biomolecules, making it difficult to quantify accurately. Several methods have been developed to study this elusive molecule, but most studies thus far have focused on those conditions that produce relatively large amounts of singlet oxygen. However, the need for more sensitive methods is required as one begins to explore the levels of singlet oxygen required in signaling and regulatory processes. Here we discuss the various methods used in the study of singlet oxygen, and outline their uses and limitations. PMID:27231787

Regulation of a polyamine transporter by the conserved 3′ UTR-derived sRNA SorX confers resistance to singlet oxygen and organic hydroperoxides in Rhodobacter sphaeroides

PubMed Central

Peng, Tao; Berghoff, Bork A.; Oh, Jeong-Il; Weber, Lennart; Schirmer, Jasmin; Schwarz, Johannes; Glaeser, Jens; Klug, Gabriele

2016-01-01

ABSTRACT Singlet oxygen is generated by bacteriochlorophylls when light and oxygen are simultaneously present in Rhodobacter sphaeroides. Singlet oxygen triggers a specific response that is partly regulated by the alternative sigma factor RpoHI/HII. The sRNA RSs2461 has previously been identified as an RpoHI/HII-dependent sRNA and is derived from the 3′ UTR of the mRNA for an OmpR-type transcriptional regulator. Similar to the RpoHI/HII-dependent CcsR and SorY sRNAs, RSs2461 affects the resistance of R. sphaeroides against singlet oxygen and was therefore renamed here SorX. Furthermore, SorX has a strong impact on resistance against organic hydroperoxides that usually occur as secondary damages downstream of singlet oxygen. The 75-nt SorX 3′ fragment, which is generated by RNase E cleavage and highly conserved among related species, represents the functional entity. A target search identified potA mRNA, which encodes a subunit of a polyamine transporter, as a direct SorX target and stress resistance via SorX could be linked to potA. The PotABCD transporter is an uptake system for spermidine in E. coli. While spermidine is generally described as beneficial during oxidative stress, we observed significantly increased sensitivity of R. sphaeroides to organic hydroperoxides in the presence of spermidine. We therefore propose that the diminished import of spermidine, due to down-regulation of potA by SorX, counteracts oxidative stress. Together with results from other studies this underlines the importance of regulated transport to bacterial stress defense. PMID:27420112

Regulation of a polyamine transporter by the conserved 3' UTR-derived sRNA SorX confers resistance to singlet oxygen and organic hydroperoxides in Rhodobacter sphaeroides.

PubMed

Peng, Tao; Berghoff, Bork A; Oh, Jeong-Il; Weber, Lennart; Schirmer, Jasmin; Schwarz, Johannes; Glaeser, Jens; Klug, Gabriele

2016-10-02

Singlet oxygen is generated by bacteriochlorophylls when light and oxygen are simultaneously present in Rhodobacter sphaeroides. Singlet oxygen triggers a specific response that is partly regulated by the alternative sigma factor RpoHI/HII. The sRNA RSs2461 has previously been identified as an RpoHI/HII-dependent sRNA and is derived from the 3' UTR of the mRNA for an OmpR-type transcriptional regulator. Similar to the RpoHI/HII-dependent CcsR and SorY sRNAs, RSs2461 affects the resistance of R. sphaeroides against singlet oxygen and was therefore renamed here SorX. Furthermore, SorX has a strong impact on resistance against organic hydroperoxides that usually occur as secondary damages downstream of singlet oxygen. The 75-nt SorX 3' fragment, which is generated by RNase E cleavage and highly conserved among related species, represents the functional entity. A target search identified potA mRNA, which encodes a subunit of a polyamine transporter, as a direct SorX target and stress resistance via SorX could be linked to potA. The PotABCD transporter is an uptake system for spermidine in E. coli. While spermidine is generally described as beneficial during oxidative stress, we observed significantly increased sensitivity of R. sphaeroides to organic hydroperoxides in the presence of spermidine. We therefore propose that the diminished import of spermidine, due to down-regulation of potA by SorX, counteracts oxidative stress. Together with results from other studies this underlines the importance of regulated transport to bacterial stress defense.

Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components.

PubMed

Onyango, Arnold N

2016-01-01

Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant) and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity.

Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components

PubMed Central

2016-01-01

Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant) and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity. PMID:27042259

Understanding Singlet and Triplet Excitons in Acene Crystals from First Principles

NASA Astrophysics Data System (ADS)

Rangel Gordillo, Tonatiuh; Sharifzadeh, Sahar; Kronik, Leeor; Neaton, Jeffrey

2014-03-01

Singlet fission, a process in which two triplet excitons are formed from a singlet exciton, has the potential to increase the solar cell efficiencies above 100%. Efficient singlet fission has been reported in larger acene crystals, such as tetracene and pentacene, in part attributable to their low-lying triplet energies. In this work, we use many-body perturbation theory within the GW approximation and the Bethe-Salpeter equation approach to compute quasiparticle gaps, low-lying singlet and and triplet excitations, and optical absorption spectra across the entire acene family of crystals, from benzene to hexacene. We closely examine the degree of localization and charge-transfer character of the low-lying singlets and triplets, and their sensitivity to crystal environment, and discuss implications for the efficiency of singlet fission in this systems. This work supported by DOE and computational resources provided by NERSC.

Charge Transfer-Mediated Singlet Fission

NASA Astrophysics Data System (ADS)

Monahan, N.; Zhu, X.-Y.

2015-04-01

Singlet fission, the splitting of a singlet exciton into two triplet excitons in molecular materials, is interesting not only as a model many-electron problem, but also as a process with potential applications in solar energy conversion. Here we discuss limitations of the conventional four-electron and molecular dimer model in describing singlet fission in crystalline organic semiconductors, such as pentacene and tetracene. We emphasize the need to consider electronic delocalization, which is responsible for the decisive role played by the Mott-Wannier exciton, also called the charge transfer (CT) exciton, in mediating singlet fission. At the strong electronic coupling limit, the initial excitation creates a quantum superposition of singlet, CT, and triplet-pair states, and we present experimental evidence for this interpretation. We also discuss the most recent attempts at translating this mechanistic understanding into design principles for CT state-mediated intramolecular singlet fission in oligomers and polymers.

Singlet Oxygen Generation by Cyclometalated Complexes and Applications†

PubMed Central

Ashen-Garry, David; Selke, Matthias

2014-01-01

While cyclometalated complexes have been extensively studied for optoelectronic applications, these compounds also represent a relatively new class of photosensitizers for the production of singlet oxygen. Thus far, singlet oxygen generation from cyclometalated Ir and Pt complexes has been studied in detail. In this review, photophysical data for singlet oxygen generation from these complexes is presented, and the mechanism of 1O2 generation is discussed, including evidence for singlet oxygen generation via an electron transfer mechanism for some of cyclometalated Ir complexes. The period from the first report of singlet oxygen generation by a cyclometalated Ir complex in 2002 through August 2013 is covered in this review. This new class of singlet oxygen photosensitizers may prove to be rather versatile due to the ease of substitution of ancillary ligands without loss of activity. Several cyclometalated complexes have been tethered to zeolites, polystyrene, or quantum dots. Applications for photooxygenation of organic molecules, including “traditional” singlet oxygen reactions (ene reaction, [4+2] and [2+2] cycloadditions) as well as oxidative coupling of amines are presented. Potential biomedical applications are also reviewed. PMID:24344628

Phosphoprotein SAK1 is a regulator of acclimation to singlet oxygen in Chlamydomonas reinhardtii.

PubMed

Wakao, Setsuko; Chin, Brian L; Ledford, Heidi K; Dent, Rachel M; Casero, David; Pellegrini, Matteo; Merchant, Sabeeha S; Niyogi, Krishna K

2014-05-23

Singlet oxygen is a highly toxic and inevitable byproduct of oxygenic photosynthesis. The unicellular green alga Chlamydomonas reinhardtii is capable of acclimating specifically to singlet oxygen stress, but the retrograde signaling pathway from the chloroplast to the nucleus mediating this response is unknown. Here we describe a mutant, singlet oxygen acclimation knocked-out 1 (sak1), that lacks the acclimation response to singlet oxygen. Analysis of genome-wide changes in RNA abundance during acclimation to singlet oxygen revealed that SAK1 is a key regulator of the gene expression response during acclimation. The SAK1 gene encodes an uncharacterized protein with a domain conserved among chlorophytes and present in some bZIP transcription factors. The SAK1 protein is located in the cytosol, and it is induced and phosphorylated upon exposure to singlet oxygen, suggesting that it is a critical intermediate component of the retrograde signal transduction pathway leading to singlet oxygen acclimation.DOI: http://dx.doi.org/10.7554/eLife.02286.001. Copyright © 2014, Wakao et al.

Singlet oxygen generation by cyclometalated complexes and applications.

PubMed

Ashen-Garry, David; Selke, Matthias

2014-01-01

While cyclometalated complexes have been extensively studied for optoelectronic applications, these compounds also represent a relatively new class of photosensitizers for the production of singlet oxygen. Thus far, singlet oxygen generation from cyclometalated Ir and Pt complexes has been studied in detail. In this review, photophysical data for singlet oxygen generation from these complexes are presented, and the mechanism of (1) O2 generation is discussed, including evidence for singlet oxygen generation via an electron-transfer mechanism for some of cyclometalated Ir complexes. The period from the first report of singlet oxygen generation by a cyclometalated Ir complex in 2002 through August 2013 is covered in this review. This new class of singlet oxygen photosensitizers may prove to be rather versatile due to the ease of substitution of ancillary ligands without loss of activity. Several cyclometalated complexes have been tethered to zeolites, polystyrene, or quantum dots. Applications for photooxygenation of organic molecules, including "traditional" singlet oxygen reactions (ene reaction, [4 + 2] and [2 + 2] cycloadditions) as well as oxidative coupling of amines are presented. Potential biomedical applications are also reviewed. © 2013 The American Society of Photobiology.

Identification of a triplet pair intermediate in singlet exciton fission in solution

PubMed Central

Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon; Parkinson, Patrick; Herz, Laura M.; Bruzek, Matthew J.; Anthony, John; Friend, Richard H.; Walker, Brian J.

2015-01-01

Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley–Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]—tetracene we find rapid (<100 ps) formation of excimers and a slower (∼10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process. PMID:26060309

Microwave Assisted Synthesis, Physicochemical, Photophysical, Single Crystal X-ray and DFT Studies of Novel Push-Pull Chromophores.

PubMed

Khan, Salman A; Asiri, Abdullah M; Basisi, Hadi Mussa; Arshad, Muhammad Nadeem; Sharma, Kamlesh

2015-11-01

Two push-pull chromophores were synthesized by knoevenagel condensation under microwave irradiation. The structure of synthesized chromophores were established by spectroscopic (FT-IR, (1)H NMR, (13)C NMR, EI-MS) and elemental analysis. Structure of the chromophores was further conformed by X-ray crystallographic. UV-Vis and fluorescence spectroscopy measurements provided that chromophores were good absorbent and fluorescent properties. Fluorescence polarity studies demonstrated that chromophores were sensitive to the polarity of the microenvironment provided by different solvents. Physicochemical parameters, including singlet absorption, extinction coefficient, stokes shift, oscillator strength, dipole moment and flurescence quantum yield were investigated in order to explore the analytical potential of the synthesized chromophores. In addition, the total energy, frontier molecular orbitals, hardness, electron affinity, ionization energy, electrostatic potential map were also studied computationally by using density functional theoretical method.

Dynamical properties of the S =1/2 random Heisenberg chain

NASA Astrophysics Data System (ADS)

Shu, Yu-Rong; Dupont, Maxime; Yao, Dao-Xin; Capponi, Sylvain; Sandvik, Anders W.

2018-03-01

We study dynamical properties at finite temperature (T ) of Heisenberg spin chains with random antiferromagnetic exchange couplings, which realize the random singlet phase in the low-energy limit, using three complementary numerical methods: exact diagonalization, matrix-product-state algorithms, and stochastic analytic continuation of quantum Monte Carlo results in imaginary time. Specifically, we investigate the dynamic spin structure factor S (q ,ω ) and its ω →0 limit, which are closely related to inelastic neutron scattering and nuclear magnetic resonance (NMR) experiments (through the spin-lattice relaxation rate 1 /T1 ). Our study reveals a continuous narrow band of low-energy excitations in S (q ,ω ) , extending throughout the q space, instead of being restricted to q ≈0 and q ≈π as found in the uniform system. Close to q =π , the scaling properties of these excitations are well captured by the random-singlet theory, but disagreements also exist with some aspects of the predicted q dependence further away from q =π . Furthermore we also find spin diffusion effects close to q =0 that are not contained within the random-singlet theory but give non-negligible contributions to the mean 1 /T1 . To compare with NMR experiments, we consider the distribution of the local relaxation rates 1 /T1 . We show that the local 1 /T1 values are broadly distributed, approximately according to a stretched exponential. The mean 1 /T1 first decreases with T , but below a crossover temperature it starts to increase and likely diverges in the limit of a small nuclear resonance frequency ω0. Although a similar divergent behavior has been predicted and experimentally observed for the static uniform susceptibility, this divergent behavior of the mean 1 /T1 has never been experimentally observed. Indeed, we show that the divergence of the mean 1 /T1 is due to rare events in the disordered chains and is concealed in experiments, where the typical 1 /T1 value is accessed.

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling☆

PubMed Central

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-01-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2.) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. PMID:26225731

Singlet oxygen generation on porous superhydrophobic surfaces: effect of gas flow and sensitizer wetting on trapping efficiency.

PubMed

Zhao, Yuanyuan; Liu, Yang; Xu, Qianfeng; Barahman, Mark; Bartusik, Dorota; Greer, Alexander; Lyons, Alan M

2014-11-13

We describe physical-organic studies of singlet oxygen generation and transport into an aqueous solution supported on superhydrophobic surfaces on which silicon-phthalocyanine (Pc) particles are immobilized. Singlet oxygen ((1)O2) was trapped by a water-soluble anthracene compound and monitored in situ using a UV-vis spectrometer. When oxygen flows through the porous superhydrophobic surface, singlet oxygen generated in the plastron (i.e., the gas layer beneath the liquid) is transported into the solution within gas bubbles, thereby increasing the liquid-gas surface area over which singlet oxygen can be trapped. Higher photooxidation rates were achieved in flowing oxygen, as compared to when the gas in the plastron was static. Superhydrophobic surfaces were also synthesized so that the Pc particles were located in contact with, or isolated from, the aqueous solution to evaluate the relative effectiveness of singlet oxygen generated in solution and the gas phase, respectively; singlet oxygen generated on particles wetted by the solution was trapped more efficiently than singlet oxygen generated in the plastron, even in the presence of flowing oxygen gas. A mechanism is proposed that explains how Pc particle wetting, plastron gas composition and flow rate as well as gas saturation of the aqueous solution affect singlet oxygen trapping efficiency. These stable superhydrophobic surfaces, which can physically isolate the photosensitizer particles from the solution may be of practical importance for delivering singlet oxygen for water purification and medical devices.

Reevaluation of analytical methods for photogenerated singlet oxygen

PubMed Central

Nakamura, Keisuke; Ishiyama, Kirika; Ikai, Hiroyo; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi; Kohno, Masahiro

2011-01-01

The aim of the present study is to compare different analytical methods for singlet oxygen and to discuss an appropriate way to evaluate the yield of singlet oxygen photogenerated from photosensitizers. Singlet oxygen photogenerated from rose bengal was evaluated by electron spin resonance analysis using sterically hindered amines, spectrophotometric analysis of 1,3-diphenylisobenzofuran oxidation, and analysis of fluorescent probe (Singlet Oxygen Sensor Green®). All of the analytical methods could evaluate the relative yield of singlet oxygen. The sensitivity of the analytical methods was 1,3-diphenylisobenzofuran < electron spin resonance < Singlet Oxygen Sensor Green®. However, Singlet Oxygen Sensor Green® could be used only when the concentration of rose bengal was very low (<1 µM). In addition, since the absorption spectra of 1,3-diphenylisobenzofuran is considerably changed by irradiation of 405 nm laser, photosensitizers which are excited by light with a wavelength of around 400 nm such as hematoporphyrin cannot be used in the 1,3-diphenylisobenzofuran oxidation method. On the other hand, electron spin resonance analysis using a sterically hindered amine, especially 2,2,6,6-tetramethyl-4-piperidinol and 2,2,5,5-tetramethyl-3-pyrroline-3-carboxamide, had proper sensitivity and wide detectable range for the yield of photogenerated singlet oxygen. Therefore, in photodynamic therapy, it is suggested that the relative yield of singlet oxygen generated by various photosensitizers can be evaluated properly by electron spin resonance analysis. PMID:21980223

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling.

PubMed

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-12-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2(.)) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Singlet oxygen quenching and radical scavenging capacities of structurally-related flavonoids present in Zuccagnia punctata Cav.

PubMed

Vieyra, Faustino E Morán; Boggetti, Héctor J; Zampini, Iris C; Ordoñez, Roxana M; Isla, María I; Alvarez, Rosa M S; De Rosso, Veridiana; Mercadante, Adriana Z; Borsarelli, Claudio D

2009-06-01

The singlet oxygen (1O2) quenching and free radical (DPPH(*), ABTS(* +) and O2(* -)) scavenging ability of three structurally-related flavonoids (7-hydroxyflavanone HF, 2',4'-dihydroxychalcone DHC and 3,7-dihydroxyflavone DHF) present in the Argentinean native shrub Zuccagnia punctata Cav. were studied in solution by combining electrochemical and kinetic measurements, mass spectroscopy, end-point antioxidant assays and computational calculations. The results showed that the antioxidant properties of these flavonoids depend on several factors, such as their electron- and hydrogen atom donor capacity, the ionization degree of the more acidic group, solvatation effects and electrostatic interactions with the oxidant species. The theoretical calculations for both the gas and solution phases at the B3LYP level of theory for the Osanger reaction field model agreed with the experimental findings, thus supporting the characterization of the antioxidant mechanism of the Z. punctata flavonoids.

Electronic Properties of Cyclacenes from TAO-DFT

PubMed Central

Wu, Chun-Shian; Lee, Pei-Yin; Chai, Jeng-Da

2016-01-01

Owing to the presence of strong static correlation effects, accurate prediction of the electronic properties (e.g., the singlet-triplet energy gaps, vertical ionization potentials, vertical electron affinities, fundamental gaps, symmetrized von Neumann entropy, active orbital occupation numbers, and real-space representation of active orbitals) of cyclacenes with n fused benzene rings (n = 4–100) has posed a great challenge to traditional electronic structure methods. To meet the challenge, we study these properties using our newly developed thermally-assisted-occupation density functional theory (TAO-DFT), a very efficient method for the study of large systems with strong static correlation effects. Besides, to examine the role of cyclic topology, the electronic properties of cyclacenes are also compared with those of acenes. Similar to acenes, the ground states of cyclacenes are singlets for all the cases studied. In contrast to acenes, the electronic properties of cyclacenes, however, exhibit oscillatory behavior (for n ≤ 30) in the approach to the corresponding properties of acenes with increasing number of benzene rings. On the basis of the calculated orbitals and their occupation numbers, the larger cyclacenes are shown to exhibit increasing polyradical character in their ground states, with the active orbitals being mainly localized at the peripheral carbon atoms. PMID:27853249

Polymorphism influences singlet fission rates in tetracene thin films

DOE PAGES

Arias, Dylan H.; Ryerson, Joseph L.; Cook, Jasper D.; ...

2015-11-06

Here, we report the effect of crystal structure and crystallite grain size on singlet fission (SF) in polycrystalline tetracene, one of the most widely studied SF and organic semiconductor materials. SF has been comprehensively studied in one polymoprh (Tc I), but not in the other, less stable polymorph (Tc II). Using carefully controlled thermal evaporation deposition conditions and high sensitivity ultrafast transient absorption spectroscopy, we found that for large crystallite size samples, SF in nearly pure Tc II films is significantly faster than SF in Tc I films. We also discovered that crystallite size has a minimal impact on themore » SF rate in Tc II films, but a significant influence in Tc I films. Large crystallites exhibit SF times of 125 ps and 22 ps in Tc I and Tc II, respectively, whereas small crystallites have SF times of 31 ps and 33 ps. Our results demonstrate first, that attention must be paid to polymorphism in obtaining a self-consistent rate picture for SF in tetracene and second, that control of polymorphism can play a significant role towards achieving a mechanistic understanding of SF in polycrystalline systems. In this latter context we show that conventional theory based on non-covalent tetracene couplings is insufficient, thus highlighting the need for models that capture the delocalized and highly mobile nature of excited states in elucidating the full photophysical picture.« less

EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.

PubMed

Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef

2018-05-18

We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .

Note: Measuring instrument of singlet oxygen quantum yield in photodynamic effects

NASA Astrophysics Data System (ADS)

Li, Zhongwei; Zhang, Pengwei; Zang, Lixin; Qin, Feng; Zhang, Zhiguo; Zhang, Hongli

2017-06-01

Using diphenylisobenzofuran (C20H14O) as a singlet oxygen (1O2) reporter, a comparison method, which can be used to measure the singlet oxygen quantum yield (ΦΔ) of the photosensitizer quantitatively, is presented in this paper. Based on this method, an automatic measuring instrument of singlet oxygen quantum yield is developed. The singlet oxygen quantum yield of the photosensitizer hermimether and aloe-emodin is measured. It is found that the measuring results are identical to the existing ones, which verifies the validity of the measuring instrument.

Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

PubMed

Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

2017-03-06

Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Singlet Fission via an Excimer-Like Intermediate in 3,6-Bis(thiophen-2-yl)diketopyrrolopyrrole Derivatives.

PubMed

Mauck, Catherine M; Hartnett, Patrick E; Margulies, Eric A; Ma, Lin; Miller, Claire E; Schatz, George C; Marks, Tobin J; Wasielewski, Michael R

2016-09-14

Singlet fission (SF) in polycrystalline thin films of four 3,6-bis(thiophen-2-yl)diketopyrrolopyrrole (TDPP) chromophores with methyl (Me), n-hexyl (C6), triethylene glycol (TEG), and 2-ethylhexyl (EH) substituents at the 2,5-positions is found to involve an intermediate excimer-like state. The four different substituents yield four distinct intermolecular packing geometries, resulting in variable intermolecular charge transfer (CT) interactions in the solid. SF from the excimer state of Me, C6, TEG, and EH takes place in τSF = 22, 336, 195, and 1200 ps, respectively, to give triplet yields of 200%, 110%, 110%, and 70%, respectively. The transient spectra of the excimer-like state and its energetic proximity to the lowest excited singlet state in these derivatives suggests that this state may be the multiexciton (1)(T1T1) state that precedes formation of the uncorrelated triplet excitons. The excimer decay rates correlate well with the SF efficiencies and the degree of intermolecular donor-acceptor interactions resulting from π-stacking of the thiophene donor of one molecule with the DPP core acceptor in another molecule as observed in the crystal structures. Such interactions are found to also increase with the SF coupling energies, as calculated for each derivative. These structural and spectroscopic studies afford a better understanding of the electronic interactions that enhance SF in chromophores having strong intra- and intermolecular CT character.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

PubMed

Cao, Jun

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

NASA Astrophysics Data System (ADS)

Cao, Jun

2015-06-01

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: An impossible compromise?

NASA Astrophysics Data System (ADS)

Huzak, M.; Deleuze, M. S.; Hajgató, B.

2011-09-01

An analysis using the formalism of crystalline orbitals for extended systems with periodicity in one dimension demonstrates that any antiferromagnetic and half-metallic spin-polarization of the edge states in n-acenes, and more generally in zigzag graphene nanoislands and nanoribbons of finite width, would imply a spin contamination ⟨S2⟩ that increases proportionally to system size, in sharp and clear contradiction with the implications of Lieb's theorem for compensated bipartite lattices and the expected value for a singlet (S = 0) electronic ground state. Verifications on naphthalene, larger n-acenes (n = 3-10) and rectangular nanographene islands of increasing size, as well as a comparison using unrestricted Hartree-Fock theory along with basis sets of improving quality against various many-body treatments demonstrate altogether that antiferromagnetism and half-metallicity in extended graphene nanoribbons will be quenched by an exact treatment of electron correlation, at the confines of non-relativistic many-body quantum mechanics. Indeed, for singlet states, symmetry-breakings in spin-densities are necessarily the outcome of a too approximate treatment of static and dynamic electron correlation in single-determinantal approaches, such as unrestricted Hartree-Fock or Density Functional Theory. In this context, such as the size-extensive spin-contamination to which it relates, half-metallicity is thus nothing else than a methodological artefact.

Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: an impossible compromise?

PubMed

Huzak, M; Deleuze, M S; Hajgató, B

2011-09-14

An analysis using the formalism of crystalline orbitals for extended systems with periodicity in one dimension demonstrates that any antiferromagnetic and half-metallic spin-polarization of the edge states in n-acenes, and more generally in zigzag graphene nanoislands and nanoribbons of finite width, would imply a spin contamination S(2) that increases proportionally to system size, in sharp and clear contradiction with the implications of Lieb's theorem for compensated bipartite lattices and the expected value for a singlet (S = 0) electronic ground state. Verifications on naphthalene, larger n-acenes (n = 3-10) and rectangular nanographene islands of increasing size, as well as a comparison using unrestricted Hartree-Fock theory along with basis sets of improving quality against various many-body treatments demonstrate altogether that antiferromagnetism and half-metallicity in extended graphene nanoribbons will be quenched by an exact treatment of electron correlation, at the confines of non-relativistic many-body quantum mechanics. Indeed, for singlet states, symmetry-breakings in spin-densities are necessarily the outcome of a too approximate treatment of static and dynamic electron correlation in single-determinantal approaches, such as unrestricted Hartree-Fock or Density Functional Theory. In this context, such as the size-extensive spin-contamination to which it relates, half-metallicity is thus nothing else than a methodological artefact. © 2011 American Institute of Physics

Generalized valence bond description of the ground states (X(1)Σg(+)) of homonuclear pnictogen diatomic molecules: N2, P2, and As2.

PubMed

Xu, Lu T; Dunning, Thom H

2015-06-09

The ground state, X1Σg+, of N2 is a textbook example of a molecule with a triple bond consisting of one σ and two π bonds. This assignment, which is usually rationalized using molecular orbital (MO) theory, implicitly assumes that the spins of the three pairs of electrons involved in the bonds are singlet-coupled (perfect pairing). However, for a six-electron singlet state, there are five distinct ways to couple the electron spins. The generalized valence bond (GVB) wave function lifts this restriction, including all of the five spin functions for the six electrons involved in the bond. For N2, we find that the perfect pairing spin function is indeed dominant at Re but that it becomes progressively less so from N2 to P2 and As2. Although the perfect pairing spin function is still the most important spin function in P2, the importance of a quasi-atomic spin function, which singlet couples the spins of the electrons in the σ orbitals while high spin coupling those of the electrons in the π orbitals on each center, has significantly increased relative to N2 and, in As2, the perfect pairing and quasi-atomic spin couplings are on essentially the same footing. This change in the spin coupling of the electrons in the bonding orbitals down the periodic table may contribute to the rather dramatic decrease in the strengths of the Pn2 bonds from N2 to As2 as well as in the increase in their chemical reactivity and should be taken into account in more detailed analyses of the bond energies in these species. We also compare the spin coupling in N2 with that in C2, where the quasi-atomic spin coupling dominants around Re.

Device-independent parallel self-testing of two singlets

NASA Astrophysics Data System (ADS)

Wu, Xingyao; Bancal, Jean-Daniel; McKague, Matthew; Scarani, Valerio

2016-06-01

Device-independent self-testing offers the possibility of certifying the quantum state and measurements, up to local isometries, using only the statistics observed by querying uncharacterized local devices. In this paper we study parallel self-testing of two maximally entangled pairs of qubits; in particular, the local tensor product structure is not assumed but derived. We prove two criteria that achieve the desired result: a double use of the Clauser-Horne-Shimony-Holt inequality and the 3 ×3 magic square game. This demonstrate that the magic square game can only be perfectly won by measuring a two-singlet state. The tolerance to noise is well within reach of state-of-the-art experiments.

Triple-functional core-shell structured upconversion luminescent nanoparticles covalently grafted with photosensitizer for luminescent, magnetic resonance imaging and photodynamic therapy in vitro

NASA Astrophysics Data System (ADS)

Qiao, Xiao-Fei; Zhou, Jia-Cai; Xiao, Jia-Wen; Wang, Ye-Fu; Sun, Ling-Dong; Yan, Chun-Hua

2012-07-01

Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF4:Yb,Er@CaF2@SiO2-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF4:Yb,Er@CaF2 nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd3+ ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r1) and similar imaging effect.Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF4:Yb,Er@CaF2@SiO2-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF4:Yb,Er@CaF2 nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd3+ ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r1) and similar imaging effect. Electronic supplementary information (ESI) available: More TEM, emission spectra, longitudinal and transverse relaxation times, t2-weighted MR images of the as-prepared nanomaterial, and confocal fluorescent images of HeLa cells. See DOI: 10.1039/c2nr30938f

Autoamplificatory singlet oxygen generation sensitizes tumor cells for intercellular apoptosis-inducing signaling.

PubMed

Bauer, Georg

2018-06-01

Tumor cells express NADPH oxidase-1 (NOX1) in their membrane and control NOX1-based intercellular reactive oxygen and nitrogen species (ROS/RNS)-dependent apoptosis-inducing signaling through membrane-associated catalase and superoxide dismutase. of tumor cells with high concentrations of H 2 O 2 , peroxnitrite, HOCl, or increasing the concentration of cell-derived NO causes initial generation of singlet oxygen and local inactivation of membrane-associated catalase. As a result, free peroxynitrite and H 2 O 2 interact and generate secondary singlet oxygen. Inactivation of further catalase molecules by secondary singlet oxygen leads to auto-amplification of singlet oxygen generation and catalase inactivation. This allows reactivation of intercellular ROS/RNS-signaling and selective apoptosis induction in tumor cells. The initial singlet oxygen generation seems to be the critical point in this complex biochemical multistep mechanism. Initial singlet oxygen generation requires the interaction between distinct tumor cell-derived ROS and RNS and may also depend on either the induction of NO synthase expression or NOX1 activation through the FAS receptor. FAS receptor activation can be achieved by singlet oxygen. Autoamplificatory generation of singlet oxygen through the interaction between peroxynitrite and hydrogen peroxide inherits a rich potential for the establishment of synergistic effects that may be instrumental for novel approaches of tumor therapy with high selectivity towards malignant cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Measurement of antiphotooxidative properties of isoquinoline alkaloids using transient thermal lens spectroscopy

NASA Astrophysics Data System (ADS)

Hung, J.; Castillo, J.; Laboren, I.; Rodríguez, M.; Hassegawa, M.

2005-11-01

The antiphotooxidative properties of boldine and chloride berberine were studied by time-resolved thermal lensing technique. These compounds belong to isoquinoline alkaloids possessing interesting biological activity (e.g. antibacterial, antimalarial, antitumor). Antiphotooxidative properties of the alkaloids were studied by mechanism of energy transference between powerful oxidizing agents such as singlet oxygen. Singlet oxygen was produced by energy transfer from chlorophyll-sensitized photooxidation of oil by exposure of high light intensities like laser. The lifetimes of singlet oxygen in dimethylsulfoxide, methanol and water were determined to confirm the assignment of the singlet molecular oxygen O II (1Δ g) in the experiments. In order to understand the effect of the alkaloids on active oxygen species, we carried out in detail an analysis of the thermal lensing signal. It was shown that the alkaloids can act as quenchers of singlet oxygen. To demonstrate the ability of the alkaloids to act efficient singlet oxygen acceptors, we have measured the fluorescence spectra of the studied alkaloids in the presence and in the absence of singlet oxygen. The antiphotooxidative activity of boldine and chloride berberine can be explained by the ability to quench singlet oxygen.

LHC signals for singlet neutrinos from a natural warped seesaw mechanism. I

NASA Astrophysics Data System (ADS)

Agashe, Kaustubh; Du, Peizhi; Hong, Sungwoo

2018-04-01

Recently, it was shown in K. Agashe et al. [Phys. Rev. D 94, 013001 (2016), 10.1103/PhysRevD.94.013001] that a straightforward implementation of the type I seesaw mechanism in a warped extra dimensional framework is in reality a natural realization of "inverse" seesaw; i.e., the Standard Model (SM) neutrino mass is dominantly generated by exchange of pseudo-Dirac TeV-mass SM singlet neutrinos. By the AdS /CFT correspondence, this scenario is dual to these singlet particles being composites of some new strong dynamics, along with the SM Higgs boson (and possibly the top quark), with the rest of the SM particles being mostly elementary. We study signals from production of these heavy neutrinos at the Large Hadron Collider (LHC). We focus on the scenario where the strong sector has a global S U (2 )L×S U (2 )R×U (1 )X symmetry; such a left-right (LR) structure being motivated by consistency with the electroweak (EW) precision tests. The singlet neutrinos are charged under S U (2 )R×U (1 )X symmetry, thus can be produced from WR± exchange, as in four-dimensional LR symmetric models. However, the direct coupling of light quarks to WR± is negligible, due to WR± also being composite (cf. four-dimensional LR models); nonetheless, a sizable coupling can be induced by mixings among the various types of W± bosons. Furthermore, WR± decays dominantly into the singlet and composite partner of charged lepton (cf. SM lepton itself in four-dimensional LR model). This heavy charged lepton, in turn, decays into SM lepton, plus Z /Higgs , thus the latter can be used for extra identification of the signal. For a benchmark scenario with WR± of mass 2 TeV and singlet neutrino of mass 750 GeV, we find that, in both the dilepton +dijet +Higgs and trilepton +Higgs channels, significant evidence can be seen at the 14 TeV LHC for an integrated luminosity of 300 fb-1 and that even discovery is possible with slightly more luminosity.

Endothermic singlet fission is hindered by excimer formation

NASA Astrophysics Data System (ADS)

Dover, Cameron B.; Gallaher, Joseph K.; Frazer, Laszlo; Tapping, Patrick C.; Petty, Anthony J.; Crossley, Maxwell J.; Anthony, John E.; Kee, Tak W.; Schmidt, Timothy W.

2018-03-01

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Endothermic singlet fission is hindered by excimer formation.

PubMed

Dover, Cameron B; Gallaher, Joseph K; Frazer, Laszlo; Tapping, Patrick C; Petty, Anthony J; Crossley, Maxwell J; Anthony, John E; Kee, Tak W; Schmidt, Timothy W

2018-03-01

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Solid state photon upconversion utilizing thermally activated delayed fluorescence molecules as triplet sensitizer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Tony C.; Congreve, Daniel N.; Baldo, Marc A., E-mail: baldo@mit.edu

2015-07-20

The ability to upconvert light is useful for a range of applications, from biological imaging to solar cells. But modern technologies have struggled to upconvert incoherent incident light at low intensities. Here, we report solid state photon upconversion employing triplet-triplet exciton annihilation in an organic semiconductor, sensitized by a thermally activated-delayed fluorescence (TADF) dye. Compared to conventional phosphorescent sensitizers, the TADF dye maximizes the wavelength shift in upconversion due to its small singlet-triplet splitting. The efficiency of energy transfer from the TADF dye is 9.1%, and the conversion yield of sensitizer exciton pairs to singlet excitons in the annihilator ismore » 1.1%. Our results demonstrate upconversion in solid state geometries and with non-heavy metal-based sensitizer materials.« less

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

Annihilation of singlet fermionic dark matter into two photons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ettefaghi, M.M.; Moazzemi, R., E-mail: mettefaghi@qom.ac.ir, E-mail: r.moazzemi@qom.ac.ir

2013-02-01

We consider an extension of the standard model in which a singlet fermionic particle, to serve as cold dark matter, and a singlet Higgs are added. We perform a reanalysis on the free parameters. In particular, demanding a correct relic abundance of dark matter, we derive and plot the coupling of the singlet fermion with the singlet Higgs, g{sub s}, versus the dark matter mass. We analytically compute the pair annihilation cross section of singlet fermionic dark matter into two photons. The thermally averaged of this cross section is calculated for wide range of energies and plotted versus dark mattermore » mass using g{sub s} consistent with the relic abundance condition. We also compare our results with the Fermi-Lat observations.« less

Polarization-dependent exciton dynamics in tetracene single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bo; Zhang, Chunfeng, E-mail: cfzhang@nju.edu.cn; Xu, Yanqing

2014-12-28

We conduct polarization-dependent ultrafast spectroscopy to study the dynamics of singlet fission (SF) in tetracene single crystals. The spectrotemporal species for singlet and triplet excitons in transient absorption spectra are found to be strongly dependent on probe polarization. By carefully analyzing the polarization dependence, the signals contributed by different transitions related to singlet excitons have been disentangled, which is further applied to construct the correlation between dynamics of singlet and triplet excitons. The anisotropy of exciton dynamics provides an alternative approach to tackle the long-standing challenge in understanding the mechanism of singlet fission in organic semiconductors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davidson, J.

Relative and absolute populations of 19 levels in beam-foil--excited neutral helium at 0.275 MeV have been measured. The singlet angular-momentum sequences show dependences on principal quantum number consistent with n$sup -3$, but the triplet sequences do not. Singlet and triplet angular-momentum sequences show similar dependences on level excitation energy. Excitation functions for six representative levels were measured in the range 0.160 to 0.500 MeV. The absolute level populations increase with energy, whereas the neutral fraction of the beam decreases with energy. Further, the P angular-momentum levels are found to be overpopulated with respect to the S and D levels. Themore » overpopulation decreases with increasing principal quantum number.« less

Effects of the oxygenation level on formation of different reactive oxygen species during photodynamic therapy.

PubMed

Price, Michael; Heilbrun, Lance; Kessel, David

2013-01-01

We examined the effect of the oxygenation level on efficacy of two photosensitizing agents, both of which target lysosomes for photodamage, but via different photochemical pathways. Upon irradiation, the chlorin termed NPe6 forms singlet oxygen in high yield while the bacteriopheophorbide WST11 forms only oxygen radicals (in an aqueous environment). Photokilling efficacy by WST11 in cell culture was impaired when the atmospheric oxygen concentration was reduced from 20% to 1%, while photokilling by NPe6 was unaffected. Studies in a cell-free system revealed that the rates of photobleaching of these agents, as a function of the oxygenation level, were correlated with results described above. Moreover, the rate of formation of oxygen radicals by either agent was more sensitive to the level of oxygenation than was singlet oxygen formation by NPe6. These data indicate that the photochemical process that leads to oxygen radical formation is more dependent on the oxygenation level than is the pathway leading to formation of singlet oxygen. © 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.

Dynamically corrected gates for singlet-triplet spin qubits with control-dependent errors

NASA Astrophysics Data System (ADS)

Jacobson, N. Tobias; Witzel, Wayne M.; Nielsen, Erik; Carroll, Malcolm S.

2013-03-01

Magnetic field inhomogeneity due to random polarization of quasi-static local magnetic impurities is a major source of environmentally induced error for singlet-triplet double quantum dot (DQD) spin qubits. Moreover, for singlet-triplet qubits this error may depend on the applied controls. This effect is significant when a static magnetic field gradient is applied to enable full qubit control. Through a configuration interaction analysis, we observe that the dependence of the field inhomogeneity-induced error on the DQD bias voltage can vary systematically as a function of the controls for certain experimentally relevant operating regimes. To account for this effect, we have developed a straightforward prescription for adapting dynamically corrected gate sequences that assume control-independent errors into sequences that compensate for systematic control-dependent errors. We show that accounting for such errors may lead to a substantial increase in gate fidelities. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Charged excitons in a dilute two-dimensional electron gas in a high magnetic field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojs, Arkadiusz; Institute of Physics, Wroclaw University of Technology, Wroclaw 50-370,; Quinn, John J.

2000-08-15

A theory of charged excitons X{sup -} in a dilute two-dimensional (2D) electron gas in a high-magnetic field is presented. In contrast to previous calculations, three bound X{sup -} states (one singlet and two triplets) are found in a narrow and symmetric GaAs quantum well. The singlet and a ''bright'' triplet are the two optically active states observed in experiments. The bright triplet has the binding energy of about 1 meV, smaller than the singlet and a ''dark'' triplet. The interaction of bound X{sup -}'s with a dilute 2D electron gas is investigated using exact diagonalization techniques. It is foundmore » that the short-range character of the e-X{sup -} interactions effectively isolates bound X{sup -} states from a dilute e-h plasma. This results in the insensitivity of the photoluminescence spectrum to the filling factor {nu}, and a rapid decrease of the oscillator strength of the dark triplet X{sup -} as a function of {nu}{sup -1}. (c) 2000 The American Physical Society.« less

Benzoylation of Ergosterol through Nucleophilic Acyl Substitution and Subsequent Formation of Ergosterol Benzoate Endoperoxide by Reaction with Singlet Oxygen Generated by Photosensitization

ERIC Educational Resources Information Center

Roslaniec, Mary C.; Sanford, Elizabeth M.

2011-01-01

Reactive oxygen species such as singlet oxygen have been a major focus of research in medicine. The effect of singlet oxygen on sterols within biological membranes is becoming increasingly more important. Ergosterol, a vitamin D precursor, is one such sterol. The benzoylation of ergosterol and subsequent reaction with singlet oxygen to form an…

Photochemical studies and nanomolar photodynamic activities of phthalocyanines functionalized with 1,4,7-trioxanonyl moieties at their non-peripheral positions.

PubMed

Sobotta, Lukasz; Wierzchowski, Marcin; Mierzwicki, Michal; Gdaniec, Zofia; Mielcarek, Jadwiga; Persoons, Leentje; Goslinski, Tomasz; Balzarini, Jan

2016-02-01

Manganese(III), cobalt(II), copper(II), magnesium(II), zinc(II) and metal-free phthalocyanines, possessing 1,4,7-trioxanonyl substituents, at their non-peripheral positions, were subjected to photochemical, photodynamic and biological activity studies. Demetallated phthalocyanine and its metallated d-block analogues, with copper(II), cobalt(II), manganese(III) chloride, were found to be less efficient singlet oxygen generators in comparison to the zinc(II) analogue and zinc(II) phthalocyanine reference. Irradiation of several phthalocyanines for short time periods resulted in a substantially increased cytostatic activity against both suspension (leukemic/lymphoma at 85nM) and solid (cervix carcinoma at 72nM and melanoma at 81nM) tumour cell lines (up to 200-fold). Noteworthy is that enveloped viruses, such as for herpesvirus and influenza A virus, but not, non-enveloped virus strains, such as Coxsackie B4 virus and reovirus-1, exposed to irradiation in the presence of the phthalocyanines, markedly lost their infectivity potential. Copyright © 2015 Elsevier Inc. All rights reserved.

The Synthesis and Photophysical Characterization of Porphyrin Photoactive Materials for Use as Sensitizers in Organic Photovoltaics and Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Marin, Dawn Marie

Solar energy conversion and photodynamic therapy (PDT) are very different applications. However, both utilize very similar photoactive molecules called porphyrins. Porphyrins are structural analogs of chlorophyll and also function as prosthetic groups in some biological enzymes. Understanding the structure/function relationship of these molecules is crucial for enhancing the energy generation efficiency of molecular solar cells and improving chemotherapeutic activity in PDT. In this dissertation, two approaches were applied with the goal of increasing the efficiency of molecular semiconductors for these applications: the heavy atom effect and donor-acceptor molecules. We enhanced the efficiency of triplet excited state formation and singlet oxygen generation for porphyrin sensitizers using the heavy atom effect. The heavy atom effect induces spin-orbit coupling to promote intersystem crossing into the triplet state. In this study, a carbomethoxyphenyl substituent was replaced with either a bromophenyl or an iodophenyl substituent on 5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrin. The longer lifetimes obtained from the increase in the triplet excited state allow for longer exciton diffusion lengths and lower recombination rates in photovoltaics. Also, the enhanced intersystem crossing is beneficial for photodynamic therapy because it increases singlet oxygen generation, which destroys tumor cells. Optimizing photovoltaic performance and PDT efficacy can also be accomplished with donor-acceptor molecules because they have extended electronic pi bond delocalization across the molecule, which causes the molecule to absorb longer wavelengths of light. Donor-acceptor molecules should produce photovoltaic devices that absorb more of the solar spectrum and produce sensitizers that absorb wavelengths of light that can penetrate through tissues. Donor-acceptor molecules were synthesized using 5,15-bis(4-carbomethoxyphenyl)porphyrin as the acceptor and thiazolo[5,4-d]thiazole derivatives as the donor. The excited state dynamics of the heavy atom derivatives and donor-acceptor molecules were studied using UV-vis spectroscopy, steady-state emission, time-resolved and delayed photoluminescence.

Antioxidant activity, total phenolics and flavonoids contents: Should we ban in vitro screening methods?

PubMed

Granato, Daniel; Shahidi, Fereidoon; Wrolstad, Ronald; Kilmartin, Paul; Melton, Laurence D; Hidalgo, Francisco J; Miyashita, Kazuo; Camp, John van; Alasalvar, Cesarettin; Ismail, Amin B; Elmore, Stephen; Birch, Gordon G; Charalampopoulos, Dimitris; Astley, Sian B; Pegg, Ronald; Zhou, Peng; Finglas, Paul

2018-10-30

As many studies are exploring the association between ingestion of bioactive compounds and decreased risk of non-communicable diseases, the scientific community continues to show considerable interest in these compounds. In addition, as many non-nutrients with putative health benefits are reducing agents, hydrogen donors, singlet oxygen quenchers or metal chelators, measurement of antioxidant activity using in vitro assays has become very popular over recent decades. Measuring concentrations of total phenolics, flavonoids, and other compound (sub)classes using UV/Vis spectrophotometry offers a rapid chemical index, but chromatographic techniques are necessary to establish structure-activity. For bioactive purposes, in vivo models are required or, at the very least, methods that employ distinct mechanisms of action (i.e., single electron transfer, transition metal chelating ability, and hydrogen atom transfer). In this regard, better understanding and application of in vitro screening methods should help design of future research studies on 'bioactive compounds'. Copyright © 2018 Elsevier Ltd. All rights reserved.

Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.

A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

DOE PAGES

Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.; ...

2017-11-04

A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Dynamics of exciton transfer in coupled polymer chains.

PubMed

Zhang, Y L; Liu, X J; Sun, Z; An, Z

2013-05-07

The dynamics of singlet and triplet exciton transfer in coupled polymer chains are investigated within the Su-Schrieffer-Heeger+Pariser-Parr-Pople model including both electron-phonon (e-p) coupling and electron-electron (e-e) interactions, using a multi-configurational time-dependent Hartree-Fock dynamic method. In order to explain the processes involved, the effects of on-site and long-range e-e interactions on the locality of the singlet and triplet excitons are first investigated on an isolated chain. It is found that the locality of the singlet exciton decreases, while the locality of the triplet exciton increases with an increase in the on-site e-e interactions. On the other hand, an increase in the long-range e-e interaction results in a more localized singlet exciton and triplet exciton. In coupled polymer chains, we then quantitatively show the yields of singlet and triplet exciton transfer products under the same interchain coupling. It is found that the yield of singlet interchain excitons is much higher than that of triplet interchain excitons, that is to say, singlet exciton transfer is significantly easier than that for triplet excitons. This results from the fact that the singlet exciton is more delocalized than the triplet exciton. In addition, hopping of electrons with opposite spins between the coupled chains can facilitate the transfer of singlet excitons. The results are of great significance for understanding the photoelectric conversion process and developing high-power organic optoelectronic applications.

Environment-induced decoherence II. Effect of decoherence on Bell's inequality for an EPR pair

NASA Astrophysics Data System (ADS)

Venugopalan, A.; Kumar, Deepak; Ghosh, R.

1995-02-01

According to Bell's theorem, the degree of correlation between spatially separated measurements on a quantum system is limited by certain inequalities if one assumes the condition of locality. Quantum mechanics predicts that this limit can be exceeded, making it nonlocal. We analyse the effect of an environment modelled by a fluctuating magnetic field on the quantum correlations in an EPR singlet as seen in the Bell inequality. We show that in an EPR setup, the system goes from the usual ‘violation’ of Bell's inequality to a ‘non-violation’ for times larger than a characteristic time scale which is related to the parameters of the fluctuating field. We also look at these inequalities as a function of the spatial separation between the EPR pair.

Antimicrobial photodynamic inactivation: a bright new technique to kill resistant microbes

PubMed Central

Hamblin, Michael R

2016-01-01

Photodynamic therapy (PDT) uses photosensitizers (non-toxic dyes) that are activated by absorption of visible light to form reactive oxygen species (including singlet oxygen) that can oxidize biomolecules and destroy cells. Antimicrobial photodynamic inactivation (aPDI) can treat localized infections. aPDI neither causes any resistance to develop in microbes, nor is affected by existing drug resistance status. We discuss some recent developments in aPDI. New photosensitizers including polycationic conjugates, stable synthetic bacteriochlorins and functionalized fullerenes are described. The microbial killing by aPDI can be synergistically potentiated (several logs) by harmless inorganic salts via photochemistry. Genetically engineered bioluminescent microbial cells allow PDT to treat infections in animal models. Photoantimicrobials have a promising future in the face of the unrelenting increase in antibiotic resistance. PMID:27421070

Majorana surface modes of nodal topological pairings in spin-3/2 semimetals

NASA Astrophysics Data System (ADS)

Yang, Wang; Xiang, Tao; Wu, Congjun

2017-10-01

When solid state systems possess active orbital-band structures subject to spin-orbit coupling, their multicomponent electronic structures are often described in terms of effective large-spin fermion models. Their topological structures of superconductivity are beyond the framework of spin singlet and triplet Cooper pairings for spin-1/2 systems. Examples include the half-Heusler compound series of RPtBi, where R stands for a rare-earth element. Their spin-orbit coupled electronic structures are described by the Luttinger-Kohn model with effective spin-3/2 fermions and are characterized by band inversion. Recent experiments provide evidence to unconventional superconductivity in the YPtBi material with nodal spin-septet pairing. We systematically study topological pairing structures in spin-3/2 systems with the cubic group symmetries and calculate the surface Majorana spectra, which exhibit zero energy flat bands, or, cubic dispersion depending on the specific symmetry of the superconducting gap functions. The signatures of these surface states in the quasiparticle interference patterns of tunneling spectroscopy are studied, which can be tested in future experiments.

Singlet Oxygen Generation by UVA Light Exposure of Endogenous Photosensitizers

PubMed Central

Baier, Jürgen; Maisch, Tim; Maier, Max; Engel, Eva; Landthaler, Michael; Bäumler, Wolfgang

2006-01-01

UVA light (320–400 nm) has been shown to produce deleterious biological effects in tissue due to the generation of singlet oxygen by substances like flavins or urocanic acid. Riboflavin, flavin mononucleotide (FMN), flavin adenine dinucleotide (FAD), β-nicotinamide adenine dinucleotide (NAD), and β-nicotinamide adenine dinucleotide phosphate (NADP), urocanic acid, or cholesterol in solution were excited at 355 nm. Singlet oxygen was directly detected by time-resolved measurement of its luminescence at 1270 nm. NAD, NADP, and cholesterol showed no luminescence signal possibly due to the very low absorption coefficient at 355 nm. Singlet oxygen luminescence of urocanic acid was clearly detected but the signal was too weak to quantify a quantum yield. The quantum yield of singlet oxygen was precisely determined for riboflavin (ΦΔ = 0.54 ± 0.07), FMN (ΦΔ = 0.51 ± 0.07), and FAD (ΦΔ = 0.07 ± 0.02). In aerated solution, riboflavin and FMN generate more singlet oxygen than exogenous photosensitizers such as Photofrin, which are applied in photodynamic therapy to kill cancer cells. With decreasing oxygen concentration, the quantum yield of singlet oxygen generation decreased, which must be considered when assessing the role of singlet oxygen at low oxygen concentrations (inside tissue). PMID:16751234

EPR study of free radicals in non- and gamma-irradiated nutritive supplements containing anthocyanins concentrate from lyophilized red wine

NASA Astrophysics Data System (ADS)

Mladenova, Ralitsa B.; Firzov, Cyril; Yordanov, Nicola D.

2010-09-01

Nutritive supplements Enoviton, Enoviton C and Enoviton CE containing standardized anthocyanins from lyophilized red wine, vitamins (some of them) and excipients were investigated by EPR spectrometry before and after gamma-irradiation. Non-irradiated samples exhibit one singlet line with g=2.0039±0.0002, most probably due to free radicals from anthocyanins. After irradiation with 10 kGy gamma-rays, tablets of Еnoviton, Еnoviton С and Еnoviton СЕ, all exhibit complex EPR signals centered at a g-value of g=2.0034. The EPR spectrum of irradiated Enoviton is different from that of Еnoviton С or Еnoviton СЕ due to the overlap of the spectra of microcrystalline cellulose and the background singlet spectrum present in all tablets with the EPR resonance due to irradiated ascorbic acid (in Еnoviton С and Еnoviton СЕ). Gamma-induced free radicals exhibit long time stability—for a six months period the intensity of central peak decrease with 30-40%.

Defect propagation in one-, two-, and three-dimensional compounds doped by magnetic atoms

DOE PAGES

Furrer, A.; Podlesnyak, A.; Krämer, K. W.; ...

2014-10-29

Inelastic neutron scattering experiments were performed to study manganese(II) dimer excitations in the diluted one-, two-, and three-dimensional compounds CsMn xMg 1-xBr 3, K 2Mn xZn 1-xF 4, and KMn xZn 1-xF 3 (x≤0.10), respectively. The transitions from the ground-state singlet to the excited triplet, split into a doublet and a singlet due to the single-ion anisotropy, exhibit remarkable fine structures. These unusual features are attributed to local structural inhomogeneities induced by the dopant Mn atoms which act like lattice defects. Statistical models support the theoretically predicted decay of atomic displacements according to 1/r 2, 1/r, and constant (for three-,more » two-, and one-dimensional compounds, respectively) where r denotes the distance of the displaced atoms from the defect. In conclusion, the observed fine structures allow a direct determination of the local exchange interactions J, and the local intradimer distances R can be derived through the linear law dJ/dR.« less

Channel branching ratios in CH2CN- photodetachment: Rotational structure and vibrational energy redistribution in autodetachment

NASA Astrophysics Data System (ADS)

Lyle, Justin; Wedig, Olivia; Gulania, Sahil; Krylov, Anna I.; Mabbs, Richard

2017-12-01

We report photoelectron spectra of CH2CN-, recorded at photon energies between 13 460 and 15 384 cm-1, which show rapid intensity variations in particular detachment channels. The branching ratios for various spectral features reveal rotational structure associated with autodetachment from an intermediate anion state. Calculations using equation-of-motion coupled-cluster method with single and double excitations reveal the presence of two dipole-bound excited anion states (a singlet and a triplet). The computed oscillator strength for the transition to the singlet dipole-bound state provides an estimate of the autodetachment channel contribution to the total photoelectron yield. Analysis of the different spectral features allows identification of the dipole-bound and neutral vibrational levels involved in the autodetachment processes. For the most part, the autodetachment channels are consistent with the vibrational propensity rule and normal mode expectation. However, examination of the rotational structure shows that autodetachment from the ν3 (v = 1 and v = 2) levels of the dipole-bound state displays behavior counter to the normal mode expectation with the final state vibrational level belonging to a different mode.

Theoretical understanding of ruthenium(II) based fluoride sensor derived from 4,5-bis(benzimidazol-2-yl)imidazole (H3ImBzim) and bipyridine: electronic structure and binding nature.

PubMed

Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Sun, Lei; Zhang, Hong-Xing

2011-03-17

Using density functional theory (DFT) approach, we assessed the newly developed fluoride sensor: [(bpy)(2)Ru(H(3)ImBzim)](2+) (denoted as 1, where H(3)ImBzim = 4,5-bis(benzimidazol-2-yl)imidazole and byp = 2,2'-bipyridine). On the basis of our benchmark test, a PBE0 functional with a LanL2DZ basis set was chosen to explore the electronic structure of 1 in both ground and singlet excited states in acetonitrile solution. Both absorption bands at 426 and 352 nm are assigned as metal-to-ligand charge-transfer transition characters. By analyzing the difference of absorption spectrum between the binding adducts and the experimental measurement, the fluoride detection process was found to be driven by the proton transfer model, which makes 1 not only capable of detecting fluoride, but also for other Bønster base anions. And the result is in general accordance with the experimental observations. We hope the current exploration can give some knowledge about the detection mechanism of the F(-) anion sensor and provide some inspiration for the design of functional molecular detectors for F(-) anion.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Generation of singlet oxygen in fullerene-containing media: 1. Photodesorption of singlet oxygen from fullerene-containing surfaces

NASA Astrophysics Data System (ADS)

Belousova, I. M.; Belousov, V. P.; Danilov, O. B.; Ermakov, A. V.; Kiselev, V. M.; Kislyakov, I. M.; Sosnov, E. N.

2008-03-01

It is shown that upon irradiation of fullerene-containing surfaces by laser or flashlamp pulses, oxygen adsorbed by these surfaces efficiently escapes to the gas phase. The observation of luminescence pulses in the spectral region of 762 and 1268 nm confirms the presence of oxygen molecules in the excited singlet state in the desorbed oxygen. The conditions for optimisation of the efficiency of singlet-oxygen production are studied. It is shown that singlet oxygen at the concentration sufficient for obtaining operation of a fullerene-oxygen-iodine laser can be produced in this way.

Cellular redox dysfunction in the development of cardiovascular diseases.

PubMed

Kanaan, Georges N; Harper, Mary-Ellen

2017-11-01

To meet its exceptionally high energy demands, the heart relies largely on fatty acid oxidation, which then drives the oxidative phosphorylation system in mitochondria. Each day, this system produces about 6kg of ATP to sustain heart function. Fatty acid oxidation is sometimes associated with high rates of mitochondrial reactive oxygen species (ROS) production. By definition, ROS are singlet electron intermediates formed during the partial reduction of oxygen to water and they include radical and non-radical intermediates like superoxide, hydrogen peroxide and hydroxyl radical. Superoxide can also interact with nitric oxide to produce peroxynitrite that in turn can give rise to other radical or non-radical reactive nitrogen species (RNS) like nitrogen dioxide, dinitrogen trioxide and others. While mitochondrial and cellular functions can be impaired by ROS if they accumulate, under normal physiological conditions ROS are important signaling molecules in the cardiovascular system. A fine balance between ROS production and antioxidant systems, including glutathione redox, is essential in the heart; otherwise the ensuing damage can contribute to pathogenic processes, which can culminate in endothelial dysfunction, atherosclerosis, hypertension, cardiac hypertrophy, arrhythmias, myocardial ischemia/reperfusion damage, and heart failure. Here we provide a succinct review of recent findings. Copyright © 2017 Elsevier B.V. All rights reserved.

Dynamics of Singlet Fission and Electron Injection in Self-Assembled Acene Monolayers on Titanium Dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Justin C; Pace, Natalie A; Arias, Dylan H

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layermore » slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer.« less

Singlet oxygen generation during the oxidation of L-tyrosine and L-dopa with mushroom tyrosinase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyaji, Akimitsu; Kohno, Masahiro; Inoue, Yoshihiro

2016-03-18

The generation of singlet oxygen during the oxidation of tyrosine and L-dopa using mushroom tyrosinase in a phosphate buffer (pH 7.4), the model of melanin synthesis in melanocytes, was examined. The reaction was performed in the presence of 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP), an acceptor of singlet oxygen and the electron spin resonance (ESR) of the spin adduct, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy (4-oxo-TEMPO), was measured. An increase in the ESR signal attributable to 4-oxo-TEMPO was observed during the oxidation of tyrosine and L-dopa with tyrosinase, indicating the generation of singlet oxygen. The results suggest that {sup 1}O{sub 2} generation via tyrosinase-catalyzed melanin synthesis occurs in melanocyte.more » - Highlights: • Generation of singlet oxygen was observed during tyrosinase-catalyzed tyrosine oxidation. • The singlet oxygen generated when tyrosine was converted into dopachrome. • The amount of singlet oxygen is not sufficient for cell toxicity. • It decreased when the hydroxyl radicals and/or superoxide anions were trapped.« less

Phosphorescence Kinetics of Singlet Oxygen Produced by Photosensitization in Spherical Nanoparticles. Part I. Theory.

PubMed

Hovan, Andrej; Datta, Shubhashis; Kruglik, Sergei G; Jancura, Daniel; Miskovsky, Pavol; Bánó, Gregor

2018-05-24

The singlet oxygen produced by energy transfer between an excited photosensitizer (pts) and ground-state oxygen molecules plays a key role in photodynamic therapy. Different nanocarrier systems are extensively studied to promote targeted pts delivery in a host body. The phosphorescence kinetics of the singlet oxygen produced by the short laser pulse photosensitization of pts inside nanoparticles is influenced by singlet oxygen diffusion from the particles to the surrounding medium. Two theoretical models are presented in this work: a more complex numerical one and a simple analytical one. Both the models predict the time course of singlet oxygen concentration inside and outside of the spherical particles following short-pulse excitation of pts. On the basis of the comparison of the numerical and analytical results, a semiempirical analytical formula is derived to calculate the characteristic diffusion time of singlet oxygen from the nanoparticles to the surrounding solvent. The phosphorescence intensity of singlet oxygen produced in pts-loaded nanocarrier systems can be calculated as a linear combination of the two concentrations (inside and outside the particles), taking the different phosphorescence emission rate constants into account.

Synthesis, spectroscopy and computational studies of some biologically important hydroxyhaloquinolines and their novel derivatives

NASA Astrophysics Data System (ADS)

Malecki, Grzegorz; Nycz, Jacek E.; Ryrych, Ewa; Ponikiewski, Lukasz; Nowak, Maria; Kusz, Joachim; Pikies, Jerzy

2010-04-01

A series crystalline compounds of methyl and phosphinyl derivatives of 2-methylquinolin-8-ol ( 1a) and related 5,7-dichloro-2-methylquinolin-8-ol ( 1b) were quantitatively prepared and characterized by microanalysis, IR, UV-vis and multinuclear NMR spectroscopy. Five of them have been characterized by single crystal X-ray diffraction method. The known compounds, 8-methoxy-2-methylquinoline ( 2a) and 8-methoxyquinoline ( 2d), were synthesised by a new route. NMR solution spectra at ambient temperature, showed readily diagnostic H-1 and C-13 signals from methyl groups. The geometries of the studied compounds were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. In general, the predicted bond lengths and angles are in a good agreement with the values based on the X-ray crystal structure data. Electronic spectra were calculated by TDDFT method.

Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Wei; Jiang, Ning; Schwarz, W. H. Eugen

The geometric and electronic ground-state structures of six MS 4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS 4 species are compared to analogous MO 4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4, whereas low MOS=II appears in high- spin septet D 2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other moleculesmore » have intermediate MOS values, containing S 2-, S 2 2-, S2 1- (and resp. O 2--, O 1-, O 2 2-, O 2 1-) ligands, bonded by ionic, covalent and correlative contributions.« less

Anthracene-based fluorescent nanoprobes for singlet oxygen detection in biological media.

PubMed

Bresolí-Obach, Roger; Nos, Jaume; Mora, Margarita; Sagristà, Maria Lluïsa; Ruiz-González, Rubén; Nonell, Santi

2016-10-15

We have developed a novel singlet oxygen nanoprobe based on 9,10-anthracenedipropionic acid covalently bound to mesoporous silica nanoparticles. The nanoparticle protects the probe from interactions with proteins, which detract from its ability to detect singlet oxygen. In vitro studies show that the nanoprobe is internalized by cells and is distributed throughout the cytoplasm, thus being capable of detecting intracellularly-generated singlet oxygen. Copyright © 2016 Elsevier Inc. All rights reserved.

Diphotons from electroweak triplet-singlet mixing

DOE PAGES

Howe, Kiel; Knapen, Simon; Robinson, Dean J.

2016-08-23

The neutral component of a real pseudoscalar electroweak (EW) triplet can produce a diphoton excess at 750 GeV, if it is somewhat mixed with an EW singlet pseudoscalar. This triplet-singlet mixing allows for greater freedom in the diboson branching ratios than the singlet-only case, but it is still possible to probe the parameter space extensively with 300 fb -1. The charged component of the triplet is pair produced at the LHC, which results in a striking signal in the form of a pair of Wγ resonances with an irreducible rate of 0.27 fb. Other signatures include multiboson final states from cascade decaysmore » of the triplet-singlet neutral states. In conclusion, a large class of composite models feature both EW singlet and triplet pseudo-Nambu-Goldstone bosons in their spectrum, with the diboson couplings generated by axial anomalies.« less

Extending the Universal One-Loop Effective Action: heavy-light coefficients

DOE PAGES

Ellis, Sebastian A. R.; Quevillon, Jérémie; You, Tevong; ...

2017-08-16

The Universal One-Loop Effective Action (UOLEA) is a general expression for the effective action obtained by evaluating in a model-independent way the one-loop expansion of a functional path integral. It can also be used to match UV theories to their low-energy EFTs more efficiently by avoiding redundant steps in the application of functional methods, simplifying the process of obtaining Wilson coefficients of operators up to dimension six. In addition to loops involving only heavy fields, matching may require the inclusion of loops containing both heavy and light particles. Here we use the recently-developed covariant diagram technique to extend the UOLEAmore » to include heavy-light terms which retain the same universal structure as the previously-derived heavy-only terms. As an example of its application, we integrate out a heavy singlet scalar with a linear coupling to a light doublet Higgs. The extension presented here is a first step towards completing the UOLEA to incorporate all possible structures encountered in a covariant derivative expansion of the one-loop path integral.« less

Extending the Universal One-Loop Effective Action: heavy-light coefficients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ellis, Sebastian A. R.; Quevillon, Jérémie; You, Tevong

The Universal One-Loop Effective Action (UOLEA) is a general expression for the effective action obtained by evaluating in a model-independent way the one-loop expansion of a functional path integral. It can also be used to match UV theories to their low-energy EFTs more efficiently by avoiding redundant steps in the application of functional methods, simplifying the process of obtaining Wilson coefficients of operators up to dimension six. In addition to loops involving only heavy fields, matching may require the inclusion of loops containing both heavy and light particles. Here we use the recently-developed covariant diagram technique to extend the UOLEAmore » to include heavy-light terms which retain the same universal structure as the previously-derived heavy-only terms. As an example of its application, we integrate out a heavy singlet scalar with a linear coupling to a light doublet Higgs. The extension presented here is a first step towards completing the UOLEA to incorporate all possible structures encountered in a covariant derivative expansion of the one-loop path integral.« less

Ultraviolet luninescence of ScPO 4, AlPO 4, and GaPO 4 crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trukhin, Anatoly N.; Shmits, Krishjanis; Jansons, Janis L.

2013-08-29

The luminescence of self-trapped excitons (STE) was previously observed and described for the case of tetragonal-symmetry ScPO 4 single crystals in 1996 by Trukhin and Boatner. The subject band in this material is situated in the UV spectral range of ~210 nm or ~5.8 eV. In the present work, we are both expanding this earlier luminescence study and seeking to identify similar luminescence phenomena in other orthophosphate crystals i.e., AlPO 4 and GaPO 4. These efforts have proven to be successful - in spite of the structural differences between these materials and ScPO 4. Specifically we have found that formore » AlPO 4 and GaPO 4, in addition to an -quartz-like STE, there is a UV luminescence that is similar in position and decay properties to that of ScPO 4 crystals. Potentially this represents an STE in AlPO 4, and GaPO 4 crystals that is analogous to the STE of ScPO 4 and other orthophosphates. The decay kinetics of the UV luminescence of ScPO 4 were studied over a wide temperature range from 8 to 300 K, and they exhibited some unusual decay characteristics when subjected to pulses from an F 2 excimer laser (157 nm). These features could be ascribed to a triplet state of the STE that is split in a zero magnetic field. A fast decay of the STE was detected as well, and therefore, we conclude that, in addition to the slow luminescence corresponding to a transition from the triplet state, there are singlet-singlet transitions of the STE. Furthermore, time-resolved spectra of the slow and fast decay exhibit a small shift (~0.15 eV) indicating that the singlet triplet splitting is small and the corresponding wave function of the STE is widely distributed over the atoms of the ScPO 4 crystal where the STE is created.« less

Mechanism for the occurrence of paramagnetic planes within magnetically ordered cerium systems

NASA Astrophysics Data System (ADS)

Kioussis, Nicholas; Cooper, Bernard R.; Banerjea, Amitava

1988-11-01

Hybridization of moderately delocalized f electrons with band electrons gives rise to a highly anisotropic two-ion interaction. Previously it has been shown that such an interaction explains the experimentally observed unusual magnetic behavior of CeBi, yielding a phase transition from a higher-temperature type-I (↑↓) to a lower-temperature type-IA (↑↑↓↓) antiferromagnetic structure. If the hybridization-mediated interaction is the key to understanding the magnetic behavior of such moderately delocalized f-electron systems, we should expect to be able to understand on this basis the even more unusual magnetic behavior of CeSb. In CeSb, there is a sequence of magnetic structures in which the higher-temperature structures involve a periodic stacking of paramagnetic \\{001\\} planes alternating with magnetically ordered \\{001\\} planes of [001]-moment alignment. In this paper we show that such a coexistence of paramagnetic and magnetically ordered Ce3+ sites can be understood on the basis of the hybridization-mediated interionic interaction when there are cubic crystal-field (CF) interactions of comparable strength. The tendency to form paramagnetic planes is found to increase with increasing CF strength (Γ7 ground state); and the stability of the up-down paramagnetic plane arrangement at high temperatures is shown to arise from the reconciliation of the magnetic ordering with the CF interactions. We also find that for a certain range of parameters a different novel situation occurs, with a fully nonmagnetic (singlet) ground state for the Ce3+ ion. This singlet state is not Kondo-like, and occurs in such a way that the system would be expected to fluctuate between two differently polarized states, one of which is the singlet state.

Open-shell characters and second hyperpolarizabilities of one-dimensional graphene nanoflakes composed of trigonal graphene units.

PubMed

Yoneda, Kyohei; Nakano, Masayoshi; Fukui, Hitoshi; Minami, Takuya; Shigeta, Yasuteru; Kubo, Takashi; Botek, Edith; Champagne, Benoît

2011-06-20

The impact of topology on the open-shell characters and the second hyperpolarizabilities (γ) has been addressed for one-dimensional graphene nanoflakes (GNFs) composed of the smallest trigonal graphene (phenalenyl) units. The main results are: 1) These GNFs show not only diradical but also multiradical characters when increasing the number of linked units. 2) GNFs composed of an equivalent number of units can exhibit a wide range of open-shell characters-from nearly closed-shell to pure multiradical characters-depending on the linking pattern of the trigonal units. 3) This wide variation in open-shell characters is explained by their resonance structures and/or by their (HOMO-i)-(LUMO+i) gaps deduced from the orbital correlations. 4) The change in the linking structure of the units can effectively control their open-shell characters as well as their γ values, of which the longitudinal components are significantly enhanced for the singlet GNFs having intermediate open-shell characters. 5) Singlet alternately linked (AL) systems present intermediate multiradical characters even in the case of a large number of units, which creates a significant enhancement of γ with increasing the size, whereas nonalternately linked (NAL) systems, which present pure multiradical characters, possess much smaller γ values. Finally 6) by switching from the singlet to the highest spin states, the γ values of NAL systems hardly change, whereas those of AL systems exhibit large reductions. These fascinating structure-property relationships between the topology of the GNFs, their open-shell characters, and their γ values not only deepen the understanding of open-shell characters of GNFs but aim also at stimulating further design studies to achieve giant NLO responses based on open-shell graphene-like materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Singlet Oxygen-Induced Membrane Disruption and Serpin-Protease Balance in Vacuolar-Driven Cell Death.

PubMed

Koh, Eugene; Carmieli, Raanan; Mor, Avishai; Fluhr, Robert

2016-07-01

Singlet oxygen plays a role in cellular stress either by providing direct toxicity or through signaling to initiate death programs. It was therefore of interest to examine cell death, as occurs in Arabidopsis, due to differentially localized singlet oxygen photosensitizers. The photosensitizers rose bengal (RB) and acridine orange (AO) were localized to the plasmalemma and vacuole, respectively. Their photoactivation led to cell death as measured by ion leakage. Cell death could be inhibited by the singlet oxygen scavenger histidine in treatments with AO but not with RB In the case of AO treatment, the vacuolar membrane was observed to disintegrate. Concomitantly, a complex was formed between a vacuolar cell-death protease, RESPONSIVE TO DESSICATION-21 and its cognate cytoplasmic protease inhibitor ATSERPIN1. In the case of RB treatment, the tonoplast remained intact and no complex was formed. Over-expression of AtSerpin1 repressed cell death, only under AO photodynamic treatment. Interestingly, acute water stress showed accumulation of singlet oxygen as determined by fluorescence of Singlet Oxygen Sensor Green, by electron paramagnetic resonance spectroscopy and the induction of singlet oxygen marker genes. Cell death by acute water stress was inhibited by the singlet oxygen scavenger histidine and was accompanied by vacuolar collapse and the appearance of serpin-protease complex. Over-expression of AtSerpin1 also attenuated cell death under this mode of cell stress. Thus, acute water stress damage shows parallels to vacuole-mediated cell death where the generation of singlet oxygen may play a role. © 2016 American Society of Plant Biologists. All Rights Reserved.

Comparison of singlet oxygen threshold dose for PDT.

PubMed

Zhu, Timothy C; Liu, Baochang; Kim, Michele M; McMillan, Dayton; Liang, Xing; Finlay, Jarod C; Busch, Theresa M

2014-02-01

Macroscopic modeling of singlet oxygen ( 1 O 2 ) is of particular interest because it is the major cytotoxic agent causing biological effects for type II photosensitizers during PDT. We have developed a macroscopic model to calculate reacted singlet oxygen concentration ([1O2] rx for PDT. An in-vivo RIF tumor mouse model is used to correlate the necrosis depth to the calculation based on explicit PDT dosimetry of light fluence distribution, tissue optical properties, and photosensitizer concentrations. Inputs to the model include 4 photosensitizer specific photochemical parameters along with the apparent singlet oxygen threshold concentration. Photosensitizer specific model parameters are determined for several type II photosensitizers (Photofrin, BPD, and HPPH). The singlet oxygen threshold concentration is approximately 0.41 - 0.56 mM for all three photosensitizers studied, assuming that the fraction of singlet oxygen generated that interacts with the cell is ( f = 1). In comparison, value derived from other in-vivo mice studies is 0.4 mM for mTHPC. However, the singlet oxygen threshold doses were reported to be 7.9 and 12.1 mM for a multicell in-vitro EMT6/Ro spheroid model for mTHPC and Photofrin PDT, respectively. The sensitivity of threshold singlet oxygen dose for our experiment is examined. The possible influence of vascular vs. apoptotic cell killing mechanism on the singlet oxygen threshold dose is discussed using the BPD with different drug-light intervals 3 hrs vs. 15 min. The observed discrepancies between different experiments warrant further investigation to explain the cause of the difference.

Comparison of singlet oxygen threshold dose for PDT

PubMed Central

Zhu, Timothy C; Liu, Baochang; Kim, Michele M.; McMillan, Dayton; Liang, Xing; Finlay, Jarod C.; Busch, Theresa M.

2015-01-01

Macroscopic modeling of singlet oxygen (1O2) is of particular interest because it is the major cytotoxic agent causing biological effects for type II photosensitizers during PDT. We have developed a macroscopic model to calculate reacted singlet oxygen concentration ([1O2]rx for PDT. An in-vivo RIF tumor mouse model is used to correlate the necrosis depth to the calculation based on explicit PDT dosimetry of light fluence distribution, tissue optical properties, and photosensitizer concentrations. Inputs to the model include 4 photosensitizer specific photochemical parameters along with the apparent singlet oxygen threshold concentration. Photosensitizer specific model parameters are determined for several type II photosensitizers (Photofrin, BPD, and HPPH). The singlet oxygen threshold concentration is approximately 0.41 – 0.56 mM for all three photosensitizers studied, assuming that the fraction of singlet oxygen generated that interacts with the cell is (f = 1). In comparison, value derived from other in-vivo mice studies is 0.4 mM for mTHPC. However, the singlet oxygen threshold doses were reported to be 7.9 and 12.1 mM for a multicell in-vitro EMT6/Ro spheroid model for mTHPC and Photofrin PDT, respectively. The sensitivity of threshold singlet oxygen dose for our experiment is examined. The possible influence of vascular vs. apoptotic cell killing mechanism on the singlet oxygen threshold dose is discussed using the BPD with different drug-light intervals 3 hrs vs. 15 min. The observed discrepancies between different experiments warrant further investigation to explain the cause of the difference. PMID:25999651

The role of singlet oxygen and oxygen concentration in photodynamic inactivation of bacteria

PubMed Central

Maisch, Tim; Baier, Jürgen; Franz, Barbara; Maier, Max; Landthaler, Michael; Szeimies, Rolf-Markus; Bäumler, Wolfgang

2007-01-01

New antibacterial strategies are required in view of the increasing resistance of bacteria to antibiotics. One promising technique involves the photodynamic inactivation of bacteria. Upon exposure to light, a photosensitizer in bacteria can generate singlet oxygen, which oxidizes proteins or lipids, leading to bacteria death. To elucidate the oxidative processes that occur during killing of bacteria, Staphylococcus aureus was incubated with a standard photosensitizer, and the generation and decay of singlet oxygen was detected directly by its luminescence at 1,270 nm. At low bacterial concentrations, the time-resolved luminescence of singlet oxygen showed a decay time of 6 ± 2 μs, which is an intermediate time for singlet oxygen decay in phospholipids of membranes (14 ± 2 μs) and in the surrounding water (3.5 ± 0.5 μs). Obviously, at low bacterial concentrations, singlet oxygen had sufficient access to water outside of S. aureus by diffusion. Thus, singlet oxygen seems to be generated in the outer cell wall areas or in adjacent cytoplasmic membranes of S. aureus. In addition, the detection of singlet oxygen luminescence can be used as a sensor of intracellular oxygen concentration. When singlet oxygen luminescence was measured at higher bacterial concentrations, the decay time increased significantly, up to ≈40 μs, because of oxygen depletion at these concentrations. This observation is an important indicator that oxygen supply is a crucial factor in the efficacy of photodynamic inactivation of bacteria, and will be of particular significance should this approach be used against multiresistant bacteria. PMID:17431036

Singlet Oxygen-Induced Membrane Disruption and Serpin-Protease Balance in Vacuolar-Driven Cell Death1[OPEN

PubMed Central

Carmieli, Raanan; Mor, Avishai; Fluhr, Robert

2016-01-01

Singlet oxygen plays a role in cellular stress either by providing direct toxicity or through signaling to initiate death programs. It was therefore of interest to examine cell death, as occurs in Arabidopsis, due to differentially localized singlet oxygen photosensitizers. The photosensitizers rose bengal (RB) and acridine orange (AO) were localized to the plasmalemma and vacuole, respectively. Their photoactivation led to cell death as measured by ion leakage. Cell death could be inhibited by the singlet oxygen scavenger histidine in treatments with AO but not with RB. In the case of AO treatment, the vacuolar membrane was observed to disintegrate. Concomitantly, a complex was formed between a vacuolar cell-death protease, RESPONSIVE TO DESSICATION-21 and its cognate cytoplasmic protease inhibitor ATSERPIN1. In the case of RB treatment, the tonoplast remained intact and no complex was formed. Over-expression of AtSerpin1 repressed cell death, only under AO photodynamic treatment. Interestingly, acute water stress showed accumulation of singlet oxygen as determined by fluorescence of Singlet Oxygen Sensor Green, by electron paramagnetic resonance spectroscopy and the induction of singlet oxygen marker genes. Cell death by acute water stress was inhibited by the singlet oxygen scavenger histidine and was accompanied by vacuolar collapse and the appearance of serpin-protease complex. Over-expression of AtSerpin1 also attenuated cell death under this mode of cell stress. Thus, acute water stress damage shows parallels to vacuole-mediated cell death where the generation of singlet oxygen may play a role. PMID:26884487

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Jun, E-mail: caojunbnu@mail.bnu.edu.cn

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed intomore » 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.« less

Non-Zhang-Rice Singlet Character of the First Ionization State of T-CuO

NASA Astrophysics Data System (ADS)

Adolphs, Clemens P. J.; Moser, Simon; Sawatzky, George A.; Berciu, Mona

2016-02-01

We argue that tetragonal CuO (T-CuO) has the potential to finally settle long-standing modeling issues for cuprate physics. We compare the one-hole quasiparticle (qp) dispersion of T-CuO to that of cuprates, in the framework of the strongly correlated (Ud d→∞ ) limit of the three-band Emery model. Unlike in CuO2 , magnetic frustration in T-CuO breaks the C4 rotational symmetry and leads to strong deviations from the Zhang-Rice singlet picture in parts of the reciprocal space. Our results are consistent with angle-resolved photoemission spectroscopy data but in sharp contradiction to those of a one-band model previously suggested for them. These differences identify T-CuO as an ideal material to test a variety of scenarios proposed for explaining cuprate phenomenology.

New signals for vector-like down-type quark in U(1) of E_6

NASA Astrophysics Data System (ADS)

Das, Kasinath; Li, Tianjun; Nandi, S.; Rai, Santosh Kumar

2018-01-01

We consider the pair production of vector-like down-type quarks in an E_6 motivated model, where each of the produced down-type vector-like quark decays into an ordinary Standard Model light quark and a singlet scalar. Both the vector-like quark and the singlet scalar appear naturally in the E_6 model with masses at the TeV scale with a favorable choice of symmetry breaking pattern. We focus on the non-standard decay of the vector-like quark and the new scalar which decays to two photons or two gluons. We analyze the signal for the vector-like quark production in the 2γ +≥ 2j channel and show how the scalar and vector-like quark masses can be determined at the Large Hadron Collider.

Glide-plane symmetry and superconducting gap structure of iron-based superconductors

DOE PAGES

Wang, Yan; Berlijn, Tom; Hirschfeld, Peter J.; ...

2015-03-10

We consider the effect of glide-plane symmetry of the Fe-pnictogen/chalcogen layer in Fe-based superconductors on pairing in spin fluctuation models. Recent theories propose that so-called η-pairing states with nonzero total momentum can be realized and possess such exotic properties as odd parity spin singlet symmetry and time-reversal symmetry breaking. Here we show that when there is orbital weight at the Fermi level from orbitals with even and odd mirror reflection symmetry in z, η pairing is inevitable; however, we conclude from explicit calculation that the gap function appearing in observable quantities is identical to that found in earlier pseudocrystal momentummore » calculations with 1 Fe per unit cell.« less

Accurate ab initio Quartic Force Fields of Cyclic and Bent HC2N Isomers

NASA Technical Reports Server (NTRS)

Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J.

2012-01-01

Highly correlated ab initio quartic force field (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T). Dunning s correlation-consistent basis sets cc-pVXZ, X=3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schr dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by perturbation theory). On the other hand, this procedure (a QFF together with either perturbation theory or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC2N. All three isomers possess significant dipole moments, 3.05D, 3.06D, and 1.71D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

The influence of excitation radiation parameters on photosensitized generation of singlet oxygen in water

NASA Astrophysics Data System (ADS)

Il'ina, A. D.; Glazov, A. L.; Semenova, I. V.; Vasyutinskii, O. S.

2016-06-01

Photosensitized generation of singlet oxygen with the aid of Radahlorin® photosensitizer has been investigated. The dependences of the intensity of singlet oxygen phosphorescence and photosensitizer fluorescence on the excitation radiation wavelength in the range of 350-440 nm and on the irradiation dose have been obtained. The dependence of the ratio of the sensitizer fluorescence intensity at about 670 nm to the singlet oxygen phosphorescence intensity at a wavelength of 1270 nm on the excitation radiation wavelength is found to be nonmonotonic and have a minimum near the center of the absorption band on its red wing. The results obtained can be used to monitor the singlet oxygen concentration in solutions.

Long-lived nuclear spin states in rapidly rotating CH2D groups

NASA Astrophysics Data System (ADS)

Elliott, Stuart J.; Brown, Lynda J.; Dumez, Jean-Nicolas; Levitt, Malcolm H.

2016-11-01

Although monodeuterated methyl groups support proton long-lived states, hindering of the methyl rotation limits the singlet relaxation time. We demonstrate an experimental case in which the rapid rotation of the CH2D group extends the singlet lifetime but does not quench the chemical shift difference between the CH2D protons, induced by the chiral environment. Proton singlet order is accessed using Spin-Lock Induced Crossing (SLIC) experiments, showing that the singlet relaxation time TS is over 2 min, exceeding the longitudinal relaxation time T1 by a factor of more than 10. This result shows that proton singlet states may be accessible and long-lived in rapidly rotating CH2D groups.

Photochemical Dynamics of Intramolecular Singlet Fission

NASA Astrophysics Data System (ADS)

Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy

2017-06-01

Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen, and D. R. Reichman, J. Chem. Phys. 141, 074705 (2014). M. G. Mavros, D. Hait, and T. A. Van Voorhis, J. Chem. Phys. 145, 214105 (2016). V. Vaissier, and T. A. Van Voorhis, in preparation.

Photoelectron Spectroscopy of Doubly and Singly Charged Group VIB Dimetalate Anions: M2O72-, MM'072-, and M207- (M, M'=Cr, Mo, W)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhai, Hua Jin; Huang, Xin; Waters, Tom

2005-11-24

We produced both doubly and singly charged Group VIB dimetalate species-M2O7 2-, MM'O72-, and M2O7 - (M, M'=) Cr, Mo, W)susing two different experimental techniques (electrospray ionization for the doubly charged anions and laser vaporization for the singly charged anions) and investigated their electronic and geometric structures using photoelectron spectroscopy and density functional calculations. Distinct changes in the electronic and geometric structures were observed as a function of the metal and charge state. The electron binding energies of the heteronuclear dianions MM'O7 2- were observed to be roughly the average of those of their homonuclear counterparts (M2O7 2- and M'2O7more » 2-). Density functional calculations indicated that W2O7 2-, W2O7-, and W2O7 possess different ground-state structures: the dianion is highly symmetric (D3d,1A1g) with a single bridging oxo ligand, the monoanion is a doublet (C1, 2A) with two bridging oxo ligands and a radical terminal oxo ligand, whereas the neutral is a singlet (C1, 1A) with two bridging oxo ligands and a terminal peroxo ligand. The combined experimental and theoretical study provides insights into the evolution of geometric and electronic structures as a function of charge state. The clusters identified might provide insights into the possible structures of reactive species present in early transition-metal oxide catalysts that are relevant to their reactivity and catalytic function.« less

Time-resolved singlet oxygen luminescence detection under photodynamic therapy relevant conditions: comparison of ex vivo application of two photosensitizer formulations

NASA Astrophysics Data System (ADS)

Schlothauer, Jan C.; Hackbarth, Steffen; Jäger, Lutz; Drobniewski, Kai; Patel, Hemantbhai; Gorun, Sergiu M.; Röder, Beate

2012-11-01

Singlet oxygen plays a crucial role in photo-dermatology and photodynamic therapy (PDT) of cancer. Its direct observation by measuring the phosphorescence at 1270 nm, however, is still challenging due to the very low emission probability. It is especially challenging for the time-resolved detection of singlet oxygen kinetics in vivo which is of special interest for biomedical applications. Photosensitized generation of singlet oxygen, in pig ear skin as model for human skin, is investigated here. Two photosensitizers (PS) were topically applied to the pig ear skin and examined in a comparative study, which include the amphiphilic pheophorbide-a and the highly hydrophobic perfluoroalkylated zinc phthalocyanine (F64PcZn). Fluorescence microscopy indicates the exclusive accumulation of pheophorbide-a in the stratum corneum, while F64PcZn can also accumulate in deeper layers of the epidermis of the pig ear skin. The kinetics obtained with phosphorescence measurements show the singlet oxygen interaction with the PS microenvironment. Different generation sites of singlet oxygen correlate with the luminescence kinetics. The results show that singlet oxygen luminescence detection can be used as a diagnostic tool, not only for research, but also during treatment. The detection methodology is suitable for the monitoring of chemical quenchers' oxidation as well as O2 saturation at singlet oxygen concentration levels relevant to PDT treatment protocols.

Relative and absolute level populations in beam-foil-excited neutral helium

NASA Technical Reports Server (NTRS)

Davidson, J.

1975-01-01

Relative and absolute populations of 19 levels in beam-foil-excited neutral helium at 0.275 MeV have been measured. The singlet angular-momentum sequences show dependences on principal quantum number consistent with n to the -3rd power, but the triplet sequences do not. Singlet and triplet angular-momentum sequences show similar dependences on level excitation energy. Excitation functions for six representative levels were measured in the range from 0.160 to 0.500 MeV. The absolute level populations increase with energy, whereas the neutral fraction of the beam decreases with energy. Further, the P angular-momentum levels are found to be overpopulated with respect to the S and D levels. The overpopulation decreases with increasing principal quantum number.

Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases

PubMed Central

Barbatti, Mario; Aquino, Adélia J. A.; Szymczak, Jaroslaw J.; Nachtigallová, Dana; Hobza, Pavel; Lischka, Hans

2010-01-01

A comprehensive effort in photodynamical ab initio simulations of the ultrafast deactivation pathways for all five nucleobases adenine, guanine, cytosine, thymine, and uracil is reported. These simulations are based on a complete nonadiabatic surface-hopping approach using extended multiconfigurational wave functions. Even though all five nucleobases share the basic internal conversion mechanisms, the calculations show a distinct grouping into purine and pyrimidine bases as concerns the complexity of the photodynamics. The purine bases adenine and guanine represent the most simple photodeactivation mechanism with the dynamics leading along a diabatic ππ* path directly and without barrier to the conical intersection seam with the ground state. In the case of the pyrimidine bases, the dynamics starts off in much flatter regions of the ππ* energy surface due to coupling of several states. This fact prohibits a clear formation of a single reaction path. Thus, the photodynamics of the pyrimidine bases is much richer and includes also nπ* states with varying importance, depending on the actual nucleobase considered. Trapping in local minima may occur and, therefore, the deactivation time to the ground state is also much longer in these cases. Implications of these findings are discussed (i) for identifying structural possibilities where singlet/triplet transitions can occur because of sufficient retention time during the singlet dynamics and (ii) concerning the flexibility of finding other deactivation pathways in substituted pyrimidines serving as candidates for alternative nucleobases. PMID:21115845

Density Functional Theory and ab Initio Computational Evidence for Nitrosamine Photoperoxides: Hammett Substituent Effects in the Photogeneration of the Nitrooxide Intermediate.

PubMed

Greer, Edyta M; Kwon, Kitae

2018-05-20

Little attention has been focused on diradical and zwitterionic photoperoxides formed from nitrosamine compounds. Here, an attempt is made to probe the electronic character of the nitrooxide intermediate formed in photochemical reactions with triplet oxygen ( 3 O 2 ). Theoretical studies have been conducted to screen para-substituted phenyl nitrosamines. In particular, we find that electron-withdrawing substituents produce low-lying triplet nitrooxide diradicals. A clear electronic dependence in the S 0 - T 1 and S 0 - S 1 energy gaps of nitrooxides was found using Hammett plots. Computed geometries show a twisted diradical triplet nitrooxide moiety, which contrasts to the nearly flat singlet zwitterionic ground-state nitrooxide moiety; analyses of charges (natural bond order), molecular orbitals (HOMO/LUMO), and spin densities enable these assignments. Calculations predict the former triplet species is photogenerated initially from nitrosamine with O 2 . The conversion of the triplet nitrooxide diradical to the singlet ground state is an example where longer-lived zwitterionic nitrooxide structures become possible. The reaction mechanism is consistent with a zwitterionic ground-state nitrooxide playing an important role in the bimolecular oxygen-transfer reaction with phosphine and phosphite trapping agents as has been observed experimentally. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Non-photochemical production of singlet oxygen via activation of persulfate by carbon nanotubes.

PubMed

Cheng, Xin; Guo, Hongguang; Zhang, Yongli; Wu, Xiao; Liu, Yang

2017-04-15

The reaction between persulfate (PS) and carbon nanotubes (CNTs) for the degradation of 2,4-dichlorophenol (2,4-DCP) was investigated. It was demonstrated that CNTs could efficiently activate PS for the degradation of 2,4-DCP. Results suggested that the neither hydroxyl radical (OH) nor sulfate radical (SO 4 - ) was produced therein. For the first time, the generation of singlet oxygen ( 1 O 2 ) was proved by several methods including electron paramagnetic resonance spectrometry (EPR) and liquid chromatography mass spectrometry measurements. Moreover, the generation of the superoxide radical as a precursor of the singlet oxygen was also confirmed by using certain scavengers and EPR measurement, in which the presence of molecular oxygen was not required as a precursor of 1 O 2 . The efficient generation of 1 O 2 using the PS/CNTs system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral conditions with the mineralization and toxicity evaluated. A kinetic model was developed to theoretically evaluate the adsorption and oxidation of 2,4-DCP on the CNTs. Accordingly, a catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PS and CNTs, and the subsequent decomposition of this intermediate into 1 O 2 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Rational Design of Emissive NIR-Absorbing Chromophores: Rh(III) Porphyrin-Aza-BODIPY Conjugates with Orthogonal Metal-Carbon Bonds.

PubMed

Zhou, Jinfeng; Gai, Lizhi; Zhou, Zhikuan; Yang, Wu; Mack, John; Xu, Kejing; Zhao, Jianzhang; Zhao, Yue; Qiu, Hailin; Chan, Kin Shing; Shen, Zhen

2016-09-05

The facile synthesis of Group 9 Rh(III) porphyrin-aza-BODIPY conjugates that are linked through an orthogonal Rh-C(aryl) bond is reported. The conjugates combine the advantages of the near-IR (NIR) absorption and intense fluorescence of aza-BODIPY dyes with the long-lived triplet states of transition metal rhodium porphyrins. Only one emission peak centered at about 720 nm is observed, irrespective of the excitation wavelength, demonstrating that the conjugates act as unique molecules rather than as dyads. The generation of a locally excited (LE) state with intramolecular charge-transfer (ICT) character has been demonstrated by solvatochromic effects in the photophysical properties, singlet oxygen quantum yields in polar solvents, and by the results of density functional theory (DFT) calculations. In nonpolar solvents, the Rh(III) conjugates exhibit strong aza-BODIPY-centered fluorescence at around 720 nm (ΦF =17-34 %), and negligible singlet oxygen generation. In polar solvents, enhancements of the singlet-oxygen quantum yield (ΦΔ =19-27 %, λex =690 nm) have been observed. Nanosecond pulsed time-resolved absorption spectroscopy confirms that relatively long-lived triplet excited states are formed. The synthetic methodology outlined herein provides a useful strategy for the assembly of functional materials that are highly desirable for a wide range of applications in material science and biomedical fields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

de la Puente, Alejandro

In this work, I present a generalization of the Next-to-Minimal Supersymmetric Standard Model (NMSSM), with an explicit μ-term and a supersymmetric mass for the singlet superfield, as a route to alleviating the little hierarchy problem of the Minimal Supersymmetric Standard Model (MSSM). I analyze two limiting cases of the model, characterized by the size of the supersymmetric mass for the singlet superfield. The small and large limits of this mass parameter are studied, and I find that I can generate masses for the lightest neutral Higgs boson up to 140 GeV with top squarks below the TeV scale, all couplingsmore » perturbative up to the gauge unification scale, and with no need to fine tune parameters in the scalar potential. This model, which I call the S-MSSM is also embedded in a gauge-mediated supersymmetry breaking scheme. I find that even with a minimal embedding of the S-MSSM into a gauge mediated scheme, the mass for the lightest Higgs boson can easily be above 114 GeV, while keeping the top squarks below the TeV scale. Furthermore, I also study the forward-backward asymmetry in the t¯t system within the framework of the S-MSSM. For this purpose, non-renormalizable couplings between the first and third generation of quarks to scalars are introduced. The two limiting cases of the S-MSSM, characterized by the size of the supersymmetric mass for the singlet superfield is analyzed, and I find that in the region of small singlet supersymmetric mass a large asymmetry can be obtained while being consistent with constraints arising from flavor physics, quark masses and top quark decays.« less

Astrophysical constraints on singlet scalars at LHC

NASA Astrophysics Data System (ADS)

Hertzberg, Mark P.; Masoumi, Ali

2017-04-01

We consider the viability of new heavy gauge singlet scalar particles at colliders such as the LHC . Our original motivation for this study came from the possibility of a new heavy particle of mass ~ TeV decaying significantly into two photons at colliders, such as LHC, but our analysis applies more broadly. We show that there are significant constraints from astrophysics and cosmology on the simplest UV complete models that incorporate such new particles and its associated collider signal. The simplest and most obvious UV complete model that incorporates such signals is that it arises from a new singlet scalar (or pseudo-scalar) coupled to a new electrically charged and colored heavy fermion. Here we show that these new fermions (and anti-fermions) would be produced in the early universe, then form new color singlet heavy mesons with light quarks, obtain a non-negligible freeze-out abundance, and remain in kinetic equilibrium until decoupling. These heavy mesons possess interesting phenomenology, dependent on their charge, including forming new bound states with electrons and protons. We show that a significant number of these heavy states would survive for the age of the universe and an appreciable number would eventually be contained within the earth and solar system. We show that this leads to detectable consequences, including the production of highly energetic events from annihilations on earth, new spectral lines, and, spectacularly, the destabilization of stars. The lack of detection of these consequences rules out such simple UV completions, putting pressure on the viability of such new particles at LHC . To incorporate such a scalar would require either much more complicated UV completions or even further new physics that provides a decay channel for the associated fermion.

SU-E-T-191: First Principle Calculation of Quantum Yield in Photodynamic Therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abolfath, R; Guo, F; Chen, Z

Purpose: We present a first-principle method to calculate the spin transfer efficiency in oxygen induced by any photon fields especially in MeV energy range. The optical pumping is mediated through photosensitizers, e.g., porphyrin and/or ensemble of quantum dots. Methods: Under normal conditions, oxygen molecules are in the relatively non-reactive triplet state. In the presence of certain photosensitizer compounds such as porphyrins, electromagnetic radiation of specific wavelengths can excite oxygen to highly reactive singlet state. With selective uptake of photosensitizers by certain malignant cells, photon irradiation of phosensitized tumors can lead to selective killing of cancer cells. This is the basismore » of photodynamic therapy (PDT). Despite several attempts, PDT has not been clinically successful except in limited superficial cancers. Many parameters such as photon energy, conjugation with quantum dots etc. can be potentially combined with PDT in order to extend the role of PDT in cancer management. The key quantity for this optimization is the spin transfer efficiency in oxygen by any photon field. The first principle calculation model presented here, is an attempt to fill this need. We employ stochastic density matrix description of the quantum jumps and the rate equation methods in quantum optics based on Markov/Poisson processes and calculate time evolution of the population of the optically pumped singlet oxygen. Results: The results demonstrate the feasibility of our model in showing the dependence of the optical yield in generating spin-singlet oxygen on the experimental conditions. The adjustable variables can be tuned to maximize the population of the singlet oxygen hence the efficacy of the photodynamic therapy. Conclusion: The present model can be employed to fit and analyze the experimental data and possibly to assist researchers in optimizing the experimental conditions in photodynamic therapy.« less

ssDNA damage dependence from singlet oxygen concentration at photodynamic interaction

NASA Astrophysics Data System (ADS)

Klimenko, V. V.; Kaydanov, N. E.; Emelyanov, A. K.; Bogdanov, A. A.

2017-11-01

Single stranded DNA damage at photodynamic treatment with Radachlorin photosensitizer was investigated. Chemical trap method was used to evaluate generation of singlet oxygen in water solution. Interaction of singlet oxygen with ssDNA resulted into decrease of the replication activity of ssDNA. DNA stopped replicating during PCR at irradiation doses greater than 15 J/cm2 and concentration of photosensitizer [PS] = 3.8 μM. The dependence of replication activity of ssDNA on generated singlet oxygen concentration was identified.

Eclipta yellow vein virus enhances chlorophyll destruction, singlet oxygen production and alters endogenous redox status in Andrographis paniculata.

PubMed

Khan, Asifa; Luqman, Suaib; Masood, Nusrat; Singh, Dhananjay Kumar; Saeed, Sana Tabanda; Samad, Abdul

2016-07-01

The infection of Eclipta yellow vein virus [EcYVV-IN, Accession No. KC476655], recently reported for the first time, on Andrographis paniculata was studied for redox-mediated alteration mechanism in infected plants. A. paniculata, an important medicinal plant, is used in traditional Indian, Chinese and modern system of medicine. Andrographolide, one of the foremost components of this plant, is known for its varied pharmacological properties. Our investigation provides insight into the effect of virus-induced changes in the singlet oxygen quenching due to the alteration in pigment content (chlorophyll and carotenoids) as well as activation of plant secondary metabolism along with defense activation leading to changes in enzymatic and non-enzymatic redox status. Due to infection, a reduction in carotenoid content was observed which leads to reduced quenching of singlet oxygen. An increased level of enzymatic (SOD and APX) and non-enzymatic antioxidant (DPPH, FRAP, RP, NO, TAC and TP) activities were also observed in virus-infected plants with a positive correlation (>0.9). However, CAT activity was diminished which could be either due to its proteolytic degradation or inactivation by superoxide anions (O(2-.)), NO or peroxynitrite radicals. A significant (p < 0.05) increase in total phenolic content was observed in the infected plants while no considerable difference was seen in the total flavonoid content. Our results highlighted the alteration in redox status caused by virus-induced biotic stress on the plants and could be useful for understanding the after effects of viral infection This study could also be helpful in developing biomimetic methods for improving the production of secondary metabolites of pharmaceutical importance. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Spectra of eigenstates in fermionic tensor quantum mechanics

NASA Astrophysics Data System (ADS)

Klebanov, Igor R.; Milekhin, Alexey; Popov, Fedor; Tarnopolsky, Grigory

2018-05-01

We study the O (N1)×O (N2)×O (N3) symmetric quantum mechanics of 3-index Majorana fermions. When the ranks Ni are all equal, this model has a large N limit which is dominated by the melonic Feynman diagrams. We derive an integral formula which computes the number of group invariant states for any set of Ni. It is non-vanishing only when each Ni is even. For equal ranks the number of singlets exhibits rapid growth with N : it jumps from 36 in the O (4 )3 model to 595 354 780 in the O (6 )3 model. We derive bounds on the values of energy, which show that they scale at most as N3 in the large N limit, in agreement with expectations. We also show that the splitting between the lowest singlet and non-singlet states is of order 1 /N . For N3=1 the tensor model reduces to O (N1)×O (N2) fermionic matrix quantum mechanics, and we find a simple expression for the Hamiltonian in terms of the quadratic Casimir operators of the symmetry group. A similar expression is derived for the complex matrix model with S U (N1)×S U (N2)×U (1 ) symmetry. Finally, we study the N3=2 case of the tensor model, which gives a more intricate complex matrix model whose symmetry is only O (N1)×O (N2)×U (1 ). All energies are again integers in appropriate units, and we derive a concise formula for the spectrum. The fermionic matrix models we studied possess standard 't Hooft large N limits where the ground state energies are of order N2, while the energy gaps are of order 1.

Pemetrexed Singlet Versus Nonpemetrexed-Based Platinum Doublet as Second-Line Chemotherapy after First-Line Epidermal Growth Factor Receptor (EGFR) Tyrosine Kinase Inhibitor Failure in Non-small Cell Lung Cancer Patients with EGFR Mutations.

PubMed

Park, Sehhoon; Keam, Bhumsuk; Kim, Se Hyun; Kim, Ki Hwan; Kim, Yu Jung; Kim, Jin-Soo; Kim, Tae Min; Lee, Se-Hoon; Kim, Dong-Wan; Lee, Jong Seok; Heo, Dae Seog

2015-10-01

Platinum-based doublet chemotherapy is the treatment of choice for patients with non-small cell lung cancer (NSCLC); however, the role of a platinum-based doublet as second-line therapy after failure of an epidermal growth factor receptor (EGFR) tyrosine kinase inhibitor (TKI) for NSCLC patients has not yet been elucidated. The purpose of this study was to compare the clinical efficacy of pemetrexed versus a platinum-based doublet as second-line therapy after failure of EGFR TKI used as first-line therapy for NSCLC patients with EGFR mutations. We designed a multicenter retrospective cohort study of 314 NSCLC patients with EGFR mutations who received an EGFR TKI as first-line palliative chemotherapy. Our analysis included 83 patients who failed EGFR TKI therapy and received second-line cytotoxic chemotherapy. Forty-six patients were treated using a platinum-based doublet and 37 patients were treated using singlet pemetrexed. The overall response rates of patients receiving a platinum-based doublet and patients receiving pemetrexed were17.4% and 32.4%, respectively (p=0.111). The median progression-free survival (PFS) of patients receiving pemetrexed was significantly longer than that of patients receiving a platinum-based doublet (4.2 months vs. 2.7 months, respectively; p=0.008). The hazard ratio was 0.54 (95% confidence interval, 0.34 to 0.86; p=0.009). Our retrospective analysis found that second-line pemetrexed singlet therapy provided significantly prolonged PFS compared to second-line platinum-based doublet chemotherapy for NSCLC patients with EGFR mutations who failed first-line EGFR TKI. Conduct of prospective studies for confirmation of our results is warranted.

Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

PubMed

Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-07-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

Monitoring and assessment of tumor hemodynamics during pleural PDT

NASA Astrophysics Data System (ADS)

Ong, Yi Hong; Kim, Michele M.; Penjweini, Rozhin; Rodriguez, Carmen E.; Dimofte, Andrea; Finlay, Jarod C.; Busch, Theresa M.; Yodh, Arjun G.; Cengel, Keith A.; Singhal, Sunil; Zhu, Timothy C.

2017-02-01

Intrapleural photodynamic therapy (PDT) has been used in combination with lung sparing surgery to treat patients with malignant pleural mesothelioma. The light, photosensitizers and tissue oxygen are the three most important factors required by type II PDT to produce singlet oxygen, 1O2, which is the main photocytotoxic agent that damages the tumor vasculature and stimulates the body's anti-tumor immune response. Although light fluence rate and photosensitizer concentrations are routinely monitored during clinical PDT, there is so far a lack of a Food and Drug Administration (FDA)-approved non-invasive technique that can be employed clinically to monitor tissue oxygen in vivo. In this paper, we demonstrated that blood flow correlates well with tissue oxygen concentration during PDT and can be used in place of [3O2] to calculate reacted singlet oxygen concentration [1O2]rx using the macroscopic singlet oxygen model. Diffuse correlation spectroscopy (DCS) was used to monitor the change in tissue blood flow non-invasively during pleural PDT. A contact probe with three source and detectors separations, 0.4, 0.7 and 1.0-cm, was sutured to the pleural cavity wall of the patients after surgical resection of the pleural mesothelioma tumor to monitor the tissue blood flow during intraoperative PDT treatment. The changes of blood flow during PDT of 2 patients are found to be in good correlation with the treatment light fluence rate recorded by the isotropic detector placed adjacent to the DCS probe. [1O2]rx calculated based on light fluence, mean photosensitizer concentration, and relative blood flow was found to be 32% higher in patient #4 (0.50mM) than that for patient #3 (0.38mM).

A simple extension of the SM that can explain the ( g-2 ) μ anomaly, small neutrino mass and a dark matter

NASA Astrophysics Data System (ADS)

Dhargyal, Lobsang

2018-07-01

In this work we propose a simple extension of the Standard Model (SM) by adding to it eleven new particles. Three heavy lepton (f e , f μ , f τ ), singlets under {SU}{(3)}c× {SU}{(2)}L carrying respective lepton numbers, charged under U{(1)}Y with Y = ‑2 and transforming under a discrete symmetry as {f}i\\to -{f}i. One scalar (ϕ 2), a singlet under all the SM gauge groups and transforms under the discrete symmetry as {φ }2\\to -{φ }2 which does not develop a non zero vacuum-expectation-value (VEV). One more scalar (ϕ 3), a singlet under all the SM gauge groups and invariant under discrete symmetry which develops a non zero VEV (v 3) and gives masses to f i s, ϕ 2 and neutrinos. Three right handed neutrinos ({ν }{iR}) and three left handed Majorana neutrinos (s iL ). With these new additional particles added to the SM we have been able to give explanations to the long standing muon (g-2) anomaly as well as the smallness of neutrino masses by the inverse seesaw mechanism. Also in this model we have a very suitable scalar dark matter (DM) candidate in ϕ 2 with allows a mass as high as 53 GeV, although due to a large Yukawa coupling required to explain the muon (g-2), its contribution to the DM relic density turn out to be too small and so it can account only for a small fraction of the DM relic density of the Universe.

Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.

PubMed

Mooßen, Oliver; Dolg, Michael

2016-06-09

The geometric and electronic structure of the recently experimentally studied molecules ZCeF2 (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce-C and Ce-O stretching frequencies at the DFT, CASSCF, second-order Rayleigh-Schrödinger perturbation theory (RS2C), multireference configuration interaction (MRCI), as well as single, doubles, and perturbative triples coupled cluster (CCSD(T)) level are reported and compared to experimental infrared absorption data in a Ne and Ar matrix.

Singlet gradient index lens for deep in vivo multiphoton microscopy

NASA Astrophysics Data System (ADS)

Murray, Teresa A.; Levene, Michael J.

2012-02-01

Micro-optical probes, including gradient index (GRIN) lenses and microprisms, have expanded the range of in vivo multiphoton microscopy to reach previously inaccessible deep brain structures such as deep cortical layers and the underlying hippocampus in mice. Yet imaging with GRIN lenses has been fundamentally limited by large amounts of spherical aberration and the need to construct compound lenses that limit the field-of-view. Here, we demonstrate the use of 0.5-mm-diameter, 1.7-mm-long GRIN lens singlets with 0.6 numerical aperture in conjunction with a cover glass and a conventional microscope objective correction collar to balance spherical aberrations. The resulting system achieves a lateral resolution of 618 nm and an axial resolution of 5.5 μm, compared to lateral and axial resolutions of ~1 μm and ~15 μm, respectively, for compound GRIN lenses of similar diameter. Furthermore, the GRIN lens singlets display fields-of-view in excess of 150 μm, compared with a few tens of microns for compound GRIN lenses. The GRIN lens/cover glass combination presented here is easy to assemble and inexpensive enough for use as a disposable device, enabling ready adoption by the neuroscience community.

High resolution absorption spectrum of CO2between 1750 and 2000 Å. 2. Rotational analysis of two parallel-type bands assigned to the lowest electronic transition 13B2←

NASA Astrophysics Data System (ADS)

Cossart-Magos, Claudina; Launay, Françoise; Parkin, James E.

The absorption spectrum of CO2 gas between 175 and 200 nm was photographed at high resolution some years ago. This very weak spectral region proved to be extremely rich in bands showing rotational fine structure. In Part 1 [C. Cossart-Magos, F. Launay, J. E. Parkin, Mol. Phys., 75, 835 (1992), nine perpendicular-type bands were assigned to the lowest singlet-singlet transition, 11A2 ← ν'3 (b2) vibration. Here, the parallel-type bands observed at 185.7 and 175.6 nm are assigned to the lowest triplet-singlet transition, 13B2 ← TMPH0629math005 ν'2 (a1) vibration. The assignment and the rotational and spin constant values obtained are discussed in relation to previous experimental data and ab initio calculation results on the lowest excited states of CO2. The actual role of the 13B2 state in CO2 photodissociation, O(3P)+CO(X1Σ+) recombination, and O(1D) emission quenching by CO(X) molecules is reviewed.

Roles of reactive oxygen species in UVA-induced oxidation of 5,6-dihydroxyindole-2-carboxylic acid-melanin as studied by differential spectrophotometric method.

PubMed

Ito, Shosuke; Kikuta, Marina; Koike, Shota; Szewczyk, Grzegorz; Sarna, Michal; Zadlo, Andrzej; Sarna, Tadeusz; Wakamatsu, Kazumasa

2016-05-01

Eumelanin photoprotects pigmented tissues from ultraviolet (UV) damage. However, UVA-induced tanning seems to result from the photooxidation of preexisting melanin and does not contribute to photoprotection. We investigated the mechanism of UVA-induced degradation of 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-melanin taking advantage of its solubility in a neutral buffer and using a differential spectrophotometric method to detect subtle changes in its structure. Our methodology is suitable for examining the effects of various agents that interact with reactive oxygen species (ROS) to determine how ROS is involved in the UVA-induced oxidative modifications. The results show that UVA radiation induces the oxidation of DHICA to indole-5,6-quinone-2-carboxylic acid in eumelanin, which is then cleaved to form a photodegraded, pyrrolic moiety and finally to form free pyrrole-2,3,5-tricarboxylic acid. The possible involvement of superoxide radical and singlet oxygen in the oxidation was suggested. The generation and quenching of singlet oxygen by DHICA-melanin was confirmed by direct measurements of singlet oxygen phosphorescence. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Nucleon matrix elements with Nf=2+1+1 maximally twisted fermions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simon Dinter, Constantia Alexandrou, Martha Constantinou, Vincent Drach, Karl Jansen, Dru Renner

2010-06-01

We present the first lattice calculation of nucleon matrix elements using four dynamical flavors. We use the Nf=2+1+1 maximally twisted mass formulation. The renormalization is performed non-perturbatively in the RI'-MOM scheme and results are given for the vector and axial vector operators with up to one-derivative. Our calculation of the average momentum of the unpolarized non-singlet parton distribution is presented and compared to our previous results obtained from the Nf=2 case.

Noncentrosymmetric superconductor BeAu

NASA Astrophysics Data System (ADS)

Amon, A.; Svanidze, E.; Cardoso-Gil, R.; Wilson, M. N.; Rosner, H.; Bobnar, M.; Schnelle, W.; Lynn, J. W.; Gumeniuk, R.; Hennig, C.; Luke, G. M.; Borrmann, H.; Leithe-Jasper, A.; Grin, Yu.

2018-01-01

Mixed spin-singlet and spin-triplet pairing can occur in noncentrosymmetric superconductors. In this respect, a comprehensive characterization of the noncentrosymmetric superconductor BeAu was carried out. It was established that BeAu undergoes a structural phase transition from a low-temperature noncentrosymmetric FeSi structure type to a high-temperature centrosymmetric structure in the CsCl type at Ts=860 K. The low-temperature modification exhibits a superconducting transition below Tc=3.3 K. The values of lower (Hc1=32 Oe) and upper (Hc2=335 Oe) critical fields are rather small, confirming that this type-II (κG-L=2.3 ) weakly coupled (λe-p=0.5 ,Δ Ce/γnTc≈1.26 ) superconductor can be well understood within the Bardeen-Cooper-Schrieffer theory. The muon spin relaxation analysis indicates that the time-reversal symmetry is preserved when the superconducting state is entered, supporting conventional superconductivity in BeAu. From the density functional band structure calculations, a considerable contribution of the Be electrons to the superconducting state was established. On average, a rather small mass renormalization was found, consistent with the experimental data.

Electronic spectra from TDDFT and machine learning in chemical space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramakrishnan, Raghunathan; Hartmann, Mia; Tapavicza, Enrico

Due to its favorable computational efficiency, time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite inaccurate. We resolve this issue with machine learning models trained on deviations of reference second-order approximate coupled-cluster (CC2) singles and doubles spectra from TDDFT counterparts, or even from DFT gap. We applied this approach to low-lying singlet-singlet vertical electronic spectra of over 20 000 synthetically feasible small organic molecules with up to eight CONF atoms. The prediction errors decay monotonously as a function of training set size. For amore » training set of 10 000 molecules, CC2 excitation energies can be reproduced to within +/- 0.1 eV for the remaining molecules. Analysis of our spectral database via chromophore counting suggests that even higher accuracies can be achieved. Based on the evidence collected, we discuss open challenges associated with data-driven modeling of high-lying spectra and transition intensities.« less

"Dark" Singlet Oxygen and Electron Paramagnetic Resonance Spin Trapping as Convenient Tools to Assess Photolytic Drug Degradation.

PubMed

Persich, Peter; Hostyn, Steven; Joie, Céline; Winderickx, Guy; Pikkemaat, Jeroen; Romijn, Edwin P; Maes, Bert U W

2017-05-01

Forced degradation studies are an important tool for a systematic assessment of decomposition pathways and identification of reactive sites in active pharmaceutical ingredients (APIs). Two methodologies have been combined in order to provide a deeper understanding of singlet oxygen-related degradation pathways of APIs under light irradiation. First, we report that a "dark" singlet oxygen test enables the investigation of drug reactivity toward singlet oxygen independently of photolytic irradiation processes. Second, the photosensitizing properties of the API producing the singlet oxygen was proven and quantified by spin trapping and electron paramagnetic resonance analysis. A combination of these techniques is an interesting addition to the forced degradation portfolio as it can be used for (1) revealing unexpected degradation pathways of APIs due to singlet oxygen, (2) clarifying photolytic drug-drug interactions in fixed-dose combinations, and (3) synthesizing larger quantities of hardly accessible oxidative drug degradants. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Fiber-optic Singlet Oxygen [1O2 (1Δg)] Generator Device Serving as a Point Selective Sterilizer

PubMed Central

Aebisher, David; Zamadar, Matibur; Mahendran, Adaickapillai; Ghosh, Goutam; McEntee, Catherine; Greer, Alexander

2016-01-01

Traditionally, Type II heterogeneous photo-oxidations produce singlet oxygen via external irradiation of a sensitizer and external supply of ground-state oxygen. A potential improvement is reported here. A hollow-core fiber-optic device was developed with an “internal” supply of light and flowing oxygen, and a porous photosensitizer-end capped configuration. Singlet oxygen was delivered through the fiber tip. The singlet oxygen steady-state concentration in the immediate vicinity of the probe tip was ca 20 fM by N-benzoyl-DL-methionine trapping. The device is portable and the singlet oxygen-generating tip is maneuverable, which opened the door to simple disinfectant studies. Complete Escherichia coli inactivation was observed in 2 h when the singlet oxygen sensitizing probe tip was immersed in 0.1 mL aqueous samples of 0.1–4.4 × 107 cells. Photobleaching of the probe tip occurred after ca 12 h of use, requiring baking and sensitizer reloading steps for reuse. PMID:20497367

Toward the excited isoscalar meson spectrum from lattice QCD

DOE PAGES

Dudek, Jozef J.; Edwards, Robert G.; Guo, Peng; ...

2013-11-18

We report on the extraction of an excited spectrum of isoscalar mesons using lattice QCD. Calculations on several lattice volumes are performed with a range of light quark masses corresponding to pion masses down to about ~400 MeV. The distillation method enables us to evaluate the required disconnected contributions with high statistical precision for a large number of meson interpolating fields. We find relatively little mixing between light and strange in most J PC channels; one notable exception is the pseudoscalar sector where the approximate SU(3) F octet, singlet structure of the η, η' is reproduced. We extract exotic Jmore » PC states, identified as hybrid mesons in which an excited gluonic field is coupled to a color-octet qqbar pair, along with non-exotic hybrid mesons embedded in a qq¯-like spectrum.« less

Conformal amplitude hierarchy and the Poincaré disk

NASA Astrophysics Data System (ADS)

Shimada, Hirohiko

2018-02-01

The amplitude for the singlet channels in the 4-point function of the fundamental field in the conformal field theory of the 2d O(n) model is studied as a function of n. For a generic value of n, the 4-point function has infinitely many amplitudes, whose landscape can be very spiky as the higher amplitude changes its sign many times at the simple poles, which generalize the unique pole of the energy operator amplitude at n = 0. In the stadard parameterization of n by angle in unit of π, we find that the zeros and poles happen at the rational angles, forming a hierarchical tree structure inherent in the Poincaré disk. Some relation between the amplitude and the Farey path, a piecewise geodesic that visits these zeros and poles, is suggested. In this hierarchy, the symmetry of the congruence subgroup Γ(2) of SL(2, ℤ) naturally arises from the two clearly distinct even/odd classes of the rational angles, in which one respectively gets the truncated operator algebras and the logarithmic 4-point functions.

Prospects of in vivo singlet oxygen luminescence monitoring: Kinetics at different locations on living mice.

PubMed

Pfitzner, Michael; Schlothauer, Jan C; Bastien, Estelle; Hackbarth, Steffen; Bezdetnaya, Lina; Lassalle, Henri-Pierre; Röder, Beate

2016-06-01

Singlet oxygen observation is considered a valuable tool to assess and optimize PDT treatment. In complex systems, such as tumors in vivo, only the direct, time-resolved singlet oxygen luminescence detection can give reliable information about generation and interaction of singlet oxygen. Up to now, evaluation of kinetics was not possible due to insufficient signal-to-noise ratio. Here we present high signal-to-noise ratio singlet oxygen luminescence kinetics obtained in mouse tumor model under PDT relevant conditions. A highly optimized system based on a custom made laser diode excitation source and a high aperture multi-furcated fiber, utilizing a photomultiplier tube with a multi photon counting device was used. Luminescence kinetics with unsurpassed signal-to-noise ratio were gained from tumor bearing nude mice in vivo upon topic application, subcutaneous injection as well as intravenous injection of different photosensitizers (chlorin e6 and dendrimer formulations of chlorin e6). Singlet oxygen kinetics in appropriate model systems are discussed to facilitate the interpretation of complex kinetics obtained from in vivo tumor tissue. This is the first study addressing the complexity of singlet oxygen luminescence kinetics in tumor tissue. At present, further investigations are needed to fully explain the processes involved. Nevertheless, the high signal-to-noise ratio proves the applicability of direct time-resolved singlet oxygen luminescence detection as a prospective tool for monitoring photodynamic therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

X-ray induced singlet oxygen generation by nanoparticle-photosensitizer conjugates for photodynamic therapy: determination of singlet oxygen quantum yield.

PubMed

Clement, Sandhya; Deng, Wei; Camilleri, Elizabeth; Wilson, Brian C; Goldys, Ewa M

2016-01-28

Singlet oxygen is a primary cytotoxic agent in photodynamic therapy. We show that CeF3 nanoparticles, pure as well as conjugated through electrostatic interaction with the photosensitizer verteporfin, are able to generate singlet oxygen as a result of UV light and 8 keV X-ray irradiation. The X-ray stimulated singlet oxygen quantum yield was determined to be 0.79 ± 0.05 for the conjugate with 31 verteporfin molecules per CeF3 nanoparticle, the highest conjugation level used. From this result we estimate the singlet oxygen dose generated from CeF3-verteporfin conjugates for a therapeutic dose of 60 Gy of ionizing radiation at energies of 6 MeV and 30 keV to be (1.2 ± 0.7) × 10(8) and (2.0 ± 0.1) × 10(9) singlet oxygen molecules per cell, respectively. These are comparable with cytotoxic doses of 5 × 10(7)-2 × 10(9) singlet oxygen molecules per cell reported in the literature for photodynamic therapy using light activation. We confirmed that the CeF3-VP conjugates enhanced cell killing with 6 MeV radiation. This work confirms the feasibility of using X- or γ- ray activated nanoparticle-photosensitizer conjugates, either to supplement the radiation treatment of cancer, or as an independent treatment modality.

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

NASA Technical Reports Server (NTRS)

Krasnovsky, A. A. Jr; Cheng, P.; Blankenship, R. E.; Moore, T. A.; Gust, D.

1993-01-01

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

Scope and limitations of the TEMPO/EPR method for singlet oxygen detection: the misleading role of electron transfer.

PubMed

Nardi, Giacomo; Manet, Ilse; Monti, Sandra; Miranda, Miguel A; Lhiaubet-Vallet, Virginie

2014-12-01

For many biological and biomedical studies, it is essential to detect the production of (1)O2 and quantify its production yield. Among the available methods, detection of the characteristic 1270-nm phosphorescence of singlet oxygen by time-resolved near-infrared (TRNIR) emission constitutes the most direct and unambiguous approach. An alternative indirect method is electron paramagnetic resonance (EPR) in combination with a singlet oxygen probe. This is based on the detection of the TEMPO free radical formed after oxidation of TEMP (2,2,6,6-tetramethylpiperidine) by singlet oxygen. Although the TEMPO/EPR method has been widely employed, it can produce misleading data. This is demonstrated by the present study, in which the quantum yields of singlet oxygen formation obtained by TRNIR emission and by the TEMPO/EPR method are compared for a set of well-known photosensitizers. The results reveal that the TEMPO/EPR method leads to significant overestimation of singlet oxygen yield when the singlet or triplet excited state of the photosensitizer is efficiently quenched by TEMP, acting as electron donor. In such case, generation of the TEMP(+) radical cation, followed by deprotonation and reaction with molecular oxygen, gives rise to an EPR-detectable TEMPO signal that is not associated with singlet oxygen production. This knowledge is essential for an appropriate and error-free application of the TEMPO/EPR method in chemical, biological, and medical studies. Copyright © 2014 Elsevier Inc. All rights reserved.

Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshii, Hiroshi, E-mail: yoshii@nirs.go.jp; Faculty of Medical Sciences, University of Fukui, Eiheiji, Fukui 910-1193; Yoshii, Yukie, E-mail: yukiey@nirs.go.jp

Highlights: Black-Right-Pointing-Pointer Some photo-excited carotenoids have photosensitizing ability. Black-Right-Pointing-Pointer They are able to produce ROS. Black-Right-Pointing-Pointer Photo-excited fucoxanthin can produce singlet oxygen through energy transfer. -- Abstract: Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energymore » states below that of singlet oxygen, such as {beta}-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease.« less

On the possibility of singlet fission in crystalline quaterrylene

NASA Astrophysics Data System (ADS)

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-01

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (ES-2ET) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

On the possibility of singlet fission in crystalline quaterrylene.

PubMed

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-14

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E S -2E T ) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

Activation of Carbon-Hydrogen and Hydrogen-Hydrogen Bonds by Copper-Nitrenes: A Comparison of Density Functional Theory with Single- and Multireference Correlation Consistent Composite Approaches.

PubMed

Tekarli, Sammer M; Williams, T Gavin; Cundari, Thomas R

2009-11-10

The kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bonds (the former of methane) have been studied using several levels of theory: B3LYP/6-311++G(d,p), B97-1/cc-pVTZ, PBE1KCIS/cc-pVTZ, and ccCA (correlation consistent Composite Approach). The results show no significant difference among the DFT methods. All three DFT methods predict the ground state of the copper-nitrene model complex, L'Cu(NH), to be a triplet, while single reference ccCA predicts the singlet to be the ground state. The contributions to the total ccCA energy indicate that the singlet state is favored at the MP2/CBS level of theory, while electron correlation beyond this level (CCSD(T)) favors a triplet state, resulting in a close energetic balance between the two states. A multireference ccCA method is applied to the nitrene active species and supports the assignment of a singlet ground state. In general, the largest difference in the model reaction cycles between DFT and ccCA methods is for processes involving radicals and bond dissociation.

Euclidean bridge to the relativistic constituent quark model

NASA Astrophysics Data System (ADS)

Hobbs, T. J.; Alberg, Mary; Miller, Gerald A.

2017-03-01

Background: Knowledge of nucleon structure is today ever more of a precision science, with heightened theoretical and experimental activity expected in coming years. At the same time, a persistent gap lingers between theoretical approaches grounded in Euclidean methods (e.g., lattice QCD, Dyson-Schwinger equations [DSEs]) as opposed to traditional Minkowski field theories (such as light-front constituent quark models). Purpose: Seeking to bridge these complementary world views, we explore the potential of a Euclidean constituent quark model (ECQM). This formalism enables us to study the gluonic dressing of the quark-level axial-vector vertex, which we undertake as a test of the framework. Method: To access its indispensable elements with a minimum of inessential detail, we develop our ECQM using the simplified quark + scalar diquark picture of the nucleon. We construct a hyperspherical formalism involving polynomial expansions of diquark propagators to marry our ECQM with the results of Bethe-Salpeter equation (BSE) analyses, and constrain model parameters by fitting electromagnetic form factor data. Results: From this formalism, we define and compute a new quantity—the Euclidean density function (EDF)—an object that characterizes the nucleon's various charge distributions as functions of the quark's Euclidean momentum. Applying this technology and incorporating information from BSE analyses, we find the quenched dressing effect on the proton's axial-singlet charge to be small in magnitude and consistent with zero, while use of recent determinations of unquenched BSEs results in a large suppression. Conclusions: The quark + scalar diquark ECQM is a step toward a realistic quark model in Euclidean space, and needs additional refinements. The substantial effect we obtain for the impact on the axial-singlet charge of the unquenched dressed vertex compared to the quenched demands further investigation.

Precision calculations for h → WW/ZZ → 4 fermions in a singlet extension of the Standard Model with P rophecy4 f

NASA Astrophysics Data System (ADS)

Altenkamp, Lukas; Boggia, Michele; Dittmaier, Stefan

2018-04-01

We consider an extension of the Standard Model by a real singlet scalar field with a ℤ2-symmetric Lagrangian and spontaneous symmetry breaking with vacuum expectation value for the singlet. Considering the lighter of the two scalars of the theory to be the 125 GeV Higgs particle, we parametrize the scalar sector by the mass of the heavy Higgs boson, a mixing angle α, and a scalar Higgs self-coupling λ 12. Taking into account theoretical constraints from perturbativity and vacuum stability, we compute next-to-leading-order electroweak and QCD corrections to the decays h → WW/ZZ → 4 fermions of the light Higgs boson for some scenarios proposed in the literature. We formulate two renormalization schemes and investigate the conversion of the input parameters between the schemes, finding sizeable effects. Solving the renormalization-group equations for the \\overline{MS} parameters α and λ 12, we observe a significantly reduced scale and scheme dependence in the next-to-leading-order results. For some scenarios suggested in the literature, the total decay width for the process h → 4 f is computed as a function of the mixing angle and compared to the width of a corresponding Standard Model Higgs boson, revealing deviations below 10%. Differential distributions do not show significant distortions by effects beyond the Standard Model. The calculations are implemented in the Monte Carlo generator P rophecy4 f, which is ready for applications in data analyses in the framework of the singlet extension.

Mimicking the photosynthetic triplet energy-transfer relay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gust, D.; Moore, T.A.; Moore, A.L.

1993-06-30

In the reaction centers of photosynthetic organisms, chlorophyll triplet states are sometimes formed by recombination of charge-separated intermediates. These triplets are excellent sensitizers for singlet oxygen formation. Carotenoid polyenes can provide photoprotection from singlet oxygen generation by rapidly quenching chlorophyll triplet states via triplet-triplet energy transfer. Because in bacteria the reaction center carotenoid is not located adjacent to the bacteriochlorophyll special pair, which is the origin of the charge separation, it has been postulated that quenching may occur via a triplet relay involving an intermediate chlorophyll monomer. We now report the synthesis and spectroscopic study of a covalently linked carotenoidmore » (C)-porphyrin (P)-pyropheophorbide (Ppd) triad molecule which mimics this triplet relay. The pyropheophorbide singlet-state C-P-[sup 1]Ppd (generated by direct excitation or energy transfer from the attached porphyrin) undergoes intersystem crossing to the triplet C-P-[sup 3]Ppd. In oxygen-free solutions, this triplet decays to [sup 3]C-p-Ppd through a triplet-transfer relay involving an intermediate C-[sup 3]P-Ppd species. In aerated solutions, quenching of C-P-[sup 3]Ppd by the attached carotenoid competes with singlet oxygen sensitization and thus provides a degree of photoprotection. In a similar traid containing a zinc porphyrin moiety, triplet transfer is slow due to the higher energy of the C-[sup 3]P[sub Zn]-Ppd intermediate, and photoprotection via the relay is nonexistent. The triplet relay ceases to function at low temperatures in both the natural and biomimetic cases due to the endergonicity of the first step. 37 refs., 6 figs., 1 tab.« less

In-vitro singlet oxygen threshold dose at PDT with Radachlorin photosensitizer

NASA Astrophysics Data System (ADS)

Klimenko, V. V.; Shmakov, S. V.; Kaydanov, N. E.; Knyazev, N. A.; Kazakov, N. V.; Rusanov, A. A.; Bogdanov, A. A.; Dubina, M. V.

2017-07-01

In this present study we investigate the Radachlorin photosensitizer accumulation in K562 cells and Hela cells and determined the cell viability after PDT. Using the macroscopic singlet oxygen modeling and cellular photosensitizer concentration the singlet oxygen threshold doses for K562 cells and Hela cells were calculated.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canavan, G.H.

The optimal allocation of space-based interceptors (SBIs) between fixed, heavy missiles and mobile singlets can be derived from approximate expressions for the boost-phase penetration of each. Singlets can cluster before launch and have shorter burn times, which reduce their availability to SBIs by an order of magnitude. Singlet penetration decreased slowly with the number of SBIs allocated to them; heavy missile penetration falls rapidly. The allocation to the heavy missiles falls linearly with their number. The penetration of heavy and singlet missiles is proportional to their numbers and inversely proportional to their availability. 8 refs., 2 figs.

Intramolecular Singlet Fission in Oligoacene Heterodimers

DOE PAGES

Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; ...

2016-02-02

In this Communication we investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. Themore » ability to tune the energies of these materials provides a key strategy to study and design new SF materials – an important process for third generation photovoltaics.« less

Sign of the Singlet ( np)-Scattering Length, Neutron Radiative Capture by the Proton and Problem of the Virtual Level of the ( np) System

NASA Astrophysics Data System (ADS)

Lyuboshitz, V. L.; Lyuboshitz, V. V.

2011-05-01

It is shown that, taking into account the process of neutron radiative capture by the proton and the negative sign of the length of singlet ( np)-scattering ( a s = - f s (0) < 0), the singlet ( np)-scattering amplitude f s has a pole at a complex energy {widetilde{E}_s}, the real part of which is negative ({Re widetilde{E}_s < 0}) and the imaginary part is positive ({Im widetilde{E}_s > 0}). This means that a singlet state of the ( np) system, which would decay into the deuteron in the ground state and the γ quantum ("singlet deuteron") does not exist, and the pole {widetilde{E}_s} corresponds to the virtual but not true quasistationary level.

Marvel Analysis of the Measured High-resolution Rovibronic Spectra of TiO

NASA Astrophysics Data System (ADS)

McKemmish, Laura K.; Masseron, Thomas; Sheppard, Samuel; Sandeman, Elizabeth; Schofield, Zak; Furtenbacher, Tibor; Császár, Attila G.; Tennyson, Jonathan; Sousa-Silva, Clara

2017-02-01

Accurate, experimental rovibronic energy levels, with associated labels and uncertainties, are reported for 11 low-lying electronic states of the diatomic {}48{{Ti}}16{{O}} molecule, determined using the Marvel (Measured Active Rotational-Vibrational Energy Levels) algorithm. All levels are based on lines corresponding to critically reviewed and validated high-resolution experimental spectra taken from 24 literature sources. The transition data are in the 2-22,160 cm-1 region. Out of the 49,679 measured transitions, 43,885 are triplet-triplet, 5710 are singlet-singlet, and 84 are triplet-singlet transitions. A careful analysis of the resulting experimental spectroscopic network (SN) allows 48,590 transitions to be validated. The transitions determine 93 vibrational band origins of {}48{{Ti}}16{{O}}, including 71 triplet and 22 singlet ones. There are 276 (73) triplet-triplet (singlet-singlet) band-heads derived from Marvel experimental energies, 123(38) of which have never been assigned in low- or high-resolution experiments. The highest J value, where J stands for the total angular momentum, for which an energy level is validated is 163. The number of experimentally derived triplet and singlet {}48{{Ti}}16{{O}} rovibrational energy levels is 8682 and 1882, respectively. The lists of validated lines and levels for {}48{{Ti}}16{{O}} are deposited in the supporting information to this paper.

Synergism between airborne singlet oxygen and a trisubstituted olefin sulfonate for the inactivation of bacteria.

PubMed

Choudhury, Rajib; Greer, Alexander

2014-04-01

The reactivity of a trisubstituted alkene surfactant (8-methylnon-7-ene-1 sulfonate, 1) to airborne singlet oxygen in a solution containing E. coli was examined. Surfactant 1 was prepared by a Strecker-type reaction of 9-bromo-2-methylnon-2-ene with sodium sulfite. Submicellar concentrations of 1 were used that reacted with singlet oxygen by an "ene" reaction to yield two hydroperoxides (7-hydroperoxy-8-methylnon-8-ene-1 sulfonate and (E)-8-hydroperoxy-8-methylnon-6-ene-1 sulfonate) in a 4:1 ratio. Exchanging the H2O solution for D2O where the lifetime of solution-phase singlet oxygen increases by 20-fold led to an ∼2-fold increase in the yield of hydroperoxides pointing to surface activity of singlet oxygen with the surfactant in a partially solvated state. In this airborne singlet oxygen reaction, E. coli inactivation was monitored in the presence and absence of 1 and by a LIVE/DEAD cell permeabilization assay. It was shown that the surfactant has low dark toxicity with respect to the bacteria, but in the presence of airborne singlet oxygen, it produces a synergistic enhancement of the bacterial inactivation. How the ene-derived surfactant hydroperoxides can provoke (1)O2 toxicity and be of general utility is discussed.

Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide† †Electronic supplementary information (ESI) available: Steady-state UV-VIS and PL, solution transient absorption, X-ray diffraction, decay associated spectra, and TIPS Tc COOH/Al2O3/TiO2 film kinetics. See DOI: 10.1039/c7sc04688j

PubMed Central

Pace, Natalie A.; Arias, Dylan H.; Granger, Devin B.; Christensen, Steven; Anthony, John E.

2018-01-01

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layer slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer. PMID:29732084

Color-singlet production at NNLO in MCFM

DOE PAGES

Boughezal, Radja; Campbell, John M.; Ellis, R. Keith; ...

2016-12-30

We present the implementation of several color-singlet final-state processes at Next-to-Next-to Leading Order (NNLO) accuracy in QCD to the publicly available parton-level Monte Carlo program MCFM. Specifically we discuss the processesmore » $$pp\\rightarrow H$$, $$pp\\rightarrow Z$$, $$pp\\rightarrow W$$, $$pp\\rightarrow HZ$$, $$pp\\rightarrow HW$$ and $$pp\\rightarrow\\gamma\\gamma$$. Decays of the unstable bosons are fully included, resulting in a flexible fully differential Monte Carlo code. The NNLO corrections have been calculated using the non-local $N$-jettiness subtraction approach. Special attention is given to the numerical aspects of running MCFM for these processes at this order. Here, we pay particular attention to the systematic uncertainties due to the power corrections induced by the $N$-jettiness regularization scheme and the evaluation time needed to run the hybrid openMP/MPI version of MCFM at NNLO on multi-processor systems.« less

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less

Excitation energies of dissociating H2: A problematic case for the adiabatic approximation of time-dependent density functional theory

NASA Astrophysics Data System (ADS)

Gritsenko, O. V.; van Gisbergen, S. J. A.; Görling, A.; Baerends, E. J.

2000-11-01

Time-dependent density functional theory (TDDFT) is applied for calculation of the excitation energies of the dissociating H2 molecule. The standard TDDFT method of adiabatic local density approximation (ALDA) totally fails to reproduce the potential curve for the lowest excited singlet 1Σu+ state of H2. Analysis of the eigenvalue problem for the excitation energies as well as direct derivation of the exchange-correlation (xc) kernel fxc(r,r',ω) shows that ALDA fails due to breakdown of its simple spatially local approximation for the kernel. The analysis indicates a complex structure of the function fxc(r,r',ω), which is revealed in a different behavior of the various matrix elements K1c,1cxc (between the highest occupied Kohn-Sham molecular orbital ψ1 and virtual MOs ψc) as a function of the bond distance R(H-H). The effect of nonlocality of fxc(r,r') is modeled by using different expressions for the corresponding matrix elements of different orbitals. Asymptotically corrected ALDA (ALDA-AC) expressions for the matrix elements K12,12xc(στ) are proposed, while for other matrix elements the standard ALDA expressions are retained. This approach provides substantial improvement over the standard ALDA. In particular, the ALDA-AC curve for the lowest singlet excitation qualitatively reproduces the shape of the exact curve. It displays a minimum and approaches a relatively large positive energy at large R(H-H). ALDA-AC also produces a substantial improvement for the calculated lowest triplet excitation, which is known to suffer from the triplet instability problem of the restricted KS ground state. Failure of the ALDA for the excitation energies is related to the failure of the local density as well as generalized gradient approximations to reproduce correctly the polarizability of dissociating H2. The expression for the response function χ is derived to show the origin of the field-counteracting term in the xc potential, which is lacking in the local density and generalized gradient approximations and which is required to obtain a correct polarizability.

Insights into the deactivation of 5-bromouracil after ultraviolet excitation

NASA Astrophysics Data System (ADS)

Peccati, Francesca; Mai, Sebastian; González, Leticia

2017-03-01

5-Bromouracil is a nucleobase analogue that can replace thymine in DNA strands and acts as a strong radiosensitizer, with potential applications in molecular biology and cancer therapy. Here, the deactivation of 5-bromouracil after ultraviolet irradiation is investigated in the singlet and triplet manifold by accurate quantum chemistry calculations and non-adiabatic dynamics simulations. It is found that, after irradiation to the bright ππ* state, three main relaxation pathways are, in principle, possible: relaxation back to the ground state, intersystem crossing (ISC) and C-Br photodissociation. Based on accurate MS-CASPT2 optimizations, we propose that ground-state relaxation should be the predominant deactivation pathway in the gas phase. We then employ different electronic structure methods to assess their suitability to carry out excited-state dynamics simulations. MRCIS (multi-reference configuration interaction including single excitations) was used in surface hopping simulations to compute the ultrafast ISC dynamics, which mostly involves the 1nOπ* and 3ππ* states. This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.

Insights into the deactivation of 5-bromouracil after ultraviolet excitation

PubMed Central

2017-01-01

5-Bromouracil is a nucleobase analogue that can replace thymine in DNA strands and acts as a strong radiosensitizer, with potential applications in molecular biology and cancer therapy. Here, the deactivation of 5-bromouracil after ultraviolet irradiation is investigated in the singlet and triplet manifold by accurate quantum chemistry calculations and non-adiabatic dynamics simulations. It is found that, after irradiation to the bright ππ* state, three main relaxation pathways are, in principle, possible: relaxation back to the ground state, intersystem crossing (ISC) and C–Br photodissociation. Based on accurate MS-CASPT2 optimizations, we propose that ground-state relaxation should be the predominant deactivation pathway in the gas phase. We then employ different electronic structure methods to assess their suitability to carry out excited-state dynamics simulations. MRCIS (multi-reference configuration interaction including single excitations) was used in surface hopping simulations to compute the ultrafast ISC dynamics, which mostly involves the 1nOπ* and 3ππ* states. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320905

Cold Rydberg molecules

NASA Astrophysics Data System (ADS)

Raithel, Georg

2017-04-01

Cold atomic systems have opened new frontiers in atomic and molecular physics, including several types of Rydberg molecules. Three types will be reviewed. Long-range Rydberg-ground molecules, first predicted in and observed in, are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules. A classification into Hund's cases will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction of neutral Rydberg-Rydberg molecules is dipole-dipole, while for ionic Rydberg molecules it is dipole-monopole. Higher-order terms are discussed. FUNDING: NSF (PHY-1506093), NNSF of China (61475123).

Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

PubMed

Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, Paul I; Ludvík, Jiří; Michl, Josef

2015-01-02

The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. Although the overall agreement is satisfactory, some discrepancies are noted and discussed.

A corpuscular picture of electrons in chemical bond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ando, Koji

We introduce a theory of chemical bond with a corpuscular picture of electrons. It employs a minimal set of localized electron wave packets with “floating and breathing” degrees of freedom and the spin-coupling of non-orthogonal valence-bond theory. Its accuracy for describing potential energy curves of chemical bonds in ground and excited states of spin singlet and triplet is examined.

Effect of endogenous carotenoids on “adaptive” mutation in Escherichia coli FC40

PubMed Central

Bridges, Bryn A.; Foster, Patricia L.; Timms, Andrew R.

2010-01-01

The appearance over many days of Lac+ frameshift mutations in Escherichia coli strain FC40 incubated on lactose selection plates is a classic example of apparent “adaptive” mutation in an episomal gene. We show that endogenously overproduced carotenoids reduce adaptive mutation under selective conditions by a factor of around two. Carotenoids are known to scavenge singlet oxygen suggesting that the accumulation of oxidative base damage may be an integral part of the adaptive mutation phenomenon. If so, the lesion cannot be 7,8-dihydro-8-oxoguanine since adaptive mutation in FC40 is unaffected by mutM and mutY mutations. If active oxygen species such as singlet oxygen are involved in adaptive mutation then they should also induce frameshift mutations in FC40 under non-selective conditions. We show that such mutations can be induced under non-selective conditions by protoporphyrin photosensitisation and that this photodynamic induction is reduced by a factor of just over two when endogenous carotenoids are present. We argue that the involvement of oxidative damage would in no way be inconsistent with current understanding of the mechanism of adaptive mutation and the role of DNA polymerases. PMID:11166030

Photoluminescence properties of polystyrene-hosted fluorophore thin films

NASA Astrophysics Data System (ADS)

Chakraborty, Subha; Harris, Katherine; Huang, Mengbing

2016-12-01

We report on a photo-luminescence study of four different fluorophores: Coumarin 6, 2,5-Diphenyloxazole (PPO), 1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOP) and Para-terpehnyl (PTP), doped in a polystyrene-based thin film. All of the samples are prepared by spin coating from a non-polar polymer solution at various concentrations. Their emission spectra and transient properties are characterized by photoluminescence measurements. Red-shifts in the emission spectra are observed for all four types of fluorophores as their concentration increases. We explain this phenomenon based on concentration dependence of solvatochromic effects and the results show good agreement with existing literature. We also show that the singlet-singlet annihilation processes are possibly a prevalent mechanism in the high concentration regime that affects the steady state and transient emission characteristics of the fluors. With the exception of PTP, photoluminescence quenching occurs as the fluorophore concentration in the polymer is increased. Rate equations for excited state decay mechanisms are analysed by considering different radiative and non-radiative energy transfer mechanisms. The results show consistency with our experimental observations. PTP shows the best photoluminescence results as an efficient fluor in the thin film, whereas PPO shows the strongest concentration dependent quenching and an anomalous lifetime distribution.

DNA bases ring-expanded with a cyclopentadiene free radical: a theoretical investigation of building blocks with diradical character.

PubMed

Zhao, Peiwen; Bu, Yuxiang

2016-01-14

In this work, we computationally design radical nucleobases which possess improved electronic properties, especially diradical properties through introducing a cyclopentadiene radical. We predict that the detailed electromagnetic features of base assemblies are based on the orientation of the extra five-membered cyclopentadiene ring. Broken symmetry DFT calculations take into account the relevant structures and properties. Our results reveal that both the radicalized DNA bases and the base pairs formed when they combine with their counterparts remain stable and display larger spin delocalization. The mode of embedding the cyclopentadiene free radical in the structures has some influence on the degree of π-conjugation, which results in various diradical characteristics. Single-layered radical base pairs all have an open-shell singlet ground state, but the energy difference between singlet and triplet is not significant. For two-layered radical base pairs, the situation is more complex. All of them have an open-shell state as their ground state, including an open-shell singlet state and an open-shell triplet state. That is, the majority of radical base pairs possess anti-ferromagnetic or ferromagnetic characteristics. We present here a more in-depth discussion and analyses to study the magnetic characteristics of radical bases and base pairs. As an important factor, two-layered radical base pairs also have been carefully analyzed. We hope that all the measurements and results presented here will stimulate further detailed insights into the related mechanisms in modified DNA bases and the design of better ring-expanded DNA magnetic materials.

In-vivo singlet oxygen threshold doses for PDT

PubMed Central

Zhu, Timothy C.; Kim, Michele M.; Liang, Xing; Finlay, Jarod C.; Busch, Theresa M.

2015-01-01

Objective Dosimetry of singlet oxygen (1O2) is of particular interest because it is the major cytotoxic agent causing biological effects for type-II photosensitizers during photodynamic therapy (PDT). An in-vivo model to determine the singlet oxygen threshold dose, [1O2]rx,sh, for PDT was developed. Material and methods An in-vivo radiation-induced fibrosarcoma (RIF) tumor mouse model was used to correlate the radius of necrosis to the calculation based on explicit PDT dosimetry of light fluence distribution, tissue optical properties, and photosensitizer concentrations. Inputs to the model include five photosensitizer-specific photochemical parameters along with [1O2]rx,sh. Photosensitizer-specific model parameters were determined for benzoporphyrin derivative monoacid ring A (BPD) and compared with two other type-II photosensitizers, Photofrin® and m-tetrahydroxyphenylchlorin (mTHPC) from the literature. Results The mean values (standard deviation) of the in-vivo [1O2]rx,sh are approximately 0.56 (0.26) and 0.72 (0.21) mM (or 3.6×107 and 4.6×107 singlet oxygen per cell to reduce the cell survival to 1/e) for Photofrin® and BPD, respectively, assuming that the fraction of generated singlet oxygen that interacts with the cell is 1. While the values for the photochemical parameters (ξ, σ, g, β) used for BPD were preliminary and may need further refinement, there is reasonable confidence for the values of the singlet oxygen threshold doses. Discussion In comparison, the [1O2]rx,sh value derived from in-vivo mouse study was reported to be 0.4 mM for mTHPC-PDT. However, the singlet oxygen required per cell is reported to be 9×108 per cell per 1/e fractional kill in an in-vitro mTHPC-PDT study on a rat prostate cancer cell line (MLL cells) and is reported to be 7.9 mM for a multicell in-vitro EMT6/Ro spheroid model for mTHPC-PDT. A theoretical analysis is provided to relate the number of in-vitro singlet oxygen required per cell to reach cell killing of 1/e to in-vivo singlet oxygen threshold dose (in mM). The sensitivity of threshold singlet oxygen dose for our experiment is examined. The possible influence of vascular vs. apoptotic cell killing mechanisms on the singlet oxygen threshold dose is discussed by comparing [1O2]rx,sh for BPD with 3 hr and 15 min drug-light-intervals, with the later being known to have a dominantly vascular effect. Conclusions The experimental results of threshold singlet oxygen concentration in an in-vivo RIF tumor model for Photofrin®, BPD, and mTHPC are about 20 times smaller than those observed in vitro. These results are consistent with knowledge that factors other than singlet oxygen-mediated tumor cell killing can contribute to PDT damage in-vivo. PMID:25927018

In-vivo singlet oxygen threshold doses for PDT.

PubMed

Zhu, Timothy C; Kim, Michele M; Liang, Xing; Finlay, Jarod C; Busch, Theresa M

2015-02-01

Dosimetry of singlet oxygen ( 1 O 2 ) is of particular interest because it is the major cytotoxic agent causing biological effects for type-II photosensitizers during photodynamic therapy (PDT). An in-vivo model to determine the singlet oxygen threshold dose, [ 1 O 2 ] rx,sh , for PDT was developed. An in-vivo radiation-induced fibrosarcoma (RIF) tumor mouse model was used to correlate the radius of necrosis to the calculation based on explicit PDT dosimetry of light fluence distribution, tissue optical properties, and photosensitizer concentrations. Inputs to the model include five photosensitizer-specific photochemical parameters along with [ 1 O 2 ] rx,sh . Photosensitizer-specific model parameters were determined for benzoporphyrin derivative monoacid ring A (BPD) and compared with two other type-II photosensitizers, Photofrin ® and m-tetrahydroxyphenylchlorin (mTHPC) from the literature. The mean values (standard deviation) of the in-vivo [ 1 O 2 ] rx,sh are approximately 0.56 (0.26) and 0.72 (0.21) mM (or 3.6×10 7 and 4.6×10 7 singlet oxygen per cell to reduce the cell survival to 1/e) for Photofrin ® and BPD, respectively, assuming that the fraction of generated singlet oxygen that interacts with the cell is 1. While the values for the photochemical parameters (ξ, σ, g , β) used for BPD were preliminary and may need further refinement, there is reasonable confidence for the values of the singlet oxygen threshold doses. In comparison, the [ 1 O 2 ] rx,sh value derived from in-vivo mouse study was reported to be 0.4 mM for mTHPC-PDT. However, the singlet oxygen required per cell is reported to be 9×10 8 per cell per 1/ e fractional kill in an in-vitro mTHPC-PDT study on a rat prostate cancer cell line (MLL cells) and is reported to be 7.9 mM for a multicell in-vitro EMT6/Ro spheroid model for mTHPC-PDT. A theoretical analysis is provided to relate the number of in-vitro singlet oxygen required per cell to reach cell killing of 1/ e to in-vivo singlet oxygen threshold dose (in mM). The sensitivity of threshold singlet oxygen dose for our experiment is examined. The possible influence of vascular vs. apoptotic cell killing mechanisms on the singlet oxygen threshold dose is discussed by comparing [ 1 O 2 ] rx,sh for BPD with 3 hr and 15 min drug-light-intervals, with the later being known to have a dominantly vascular effect. The experimental results of threshold singlet oxygen concentration in an in-vivo RIF tumor model for Photofrin ® , BPD, and mTHPC are about 20 times smaller than those observed in vitro . These results are consistent with knowledge that factors other than singlet oxygen-mediated tumor cell killing can contribute to PDT damage in-vivo .

Aerobic photoreactivity of synthetic eumelanins and pheomelanins: generation of singlet oxygen and superoxide anion.

PubMed

Szewczyk, Grzegorz; Zadlo, Andrzej; Sarna, Michal; Ito, Shosuke; Wakamatsu, Kazumasa; Sarna, Tadeusz

2016-11-01

In this work, we examined photoreactivity of synthetic eumelanins, formed by autooxidation of DOPA, or enzymatic oxidation of 5,6-dihydroxyindole-2-carboxylic acid and synthetic pheomelanins obtained by enzymatic oxidation of 5-S-cysteinyldopa or 1:1 mixture of DOPA and cysteine. Electron paramagnetic resonance oximetry and spin trapping were used to measure oxygen consumption and formation of superoxide anion induced by irradiation of melanin with blue light, and time-resolved near-infrared luminescence was employed to determine the photoformation of singlet oxygen between 300 and 600 nm. Both superoxide anion and singlet oxygen were photogenerated by the synthetic melanins albeit with different efficiency. At 450-nm, quantum yield of singlet oxygen was very low (~10 -4 ) but it strongly increased in the UV region. The melanins quenched singlet oxygen efficiently, indicating that photogeneration and quenching of singlet oxygen may play an important role in aerobic photochemistry of melanin pigments and could contribute to their photodegradation and photoaging. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Time-resolved spectral analysis of Radachlorin luminescence in water

NASA Astrophysics Data System (ADS)

Belik, V. P.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

2017-05-01

We report results of spectral- and time-resolved study of Radachlorin photosensitizer luminescence in water in the spectral range of 950-1350nm and for determination of the photosensitizer triplet state and the singlet oxygen lifetimes responsible for singlet oxygen generation and degradation. At any wavelength within the explored spectral range the luminescence decay contained two major contributions: a fast decay at the ns time scale and a slow evolution at the μs time scale. The fast decay was attributed to electric dipole fluorescence transitions in photosensitizer molecules and the slow evolution to intercombination phosphorescence transitions in singlet oxygen and photosensitizer molecules. Relatively high-amplitude ns peak observed at all wavelengths suggests that singlet oxygen monitoring with spectral isolation methods alone, without additional temporal resolution can be controversial. In the applied experimental conditions the total phosphorescence signal at any wavelength contained a contribution from the photosensitizer triplet state decay, while at 1274nm the singlet oxygen phosphorescence dominated. The results obtained can be used for optimization of the methods of singlet oxygen monitoring and imaging.

Microscopic time-resolved imaging of singlet oxygen by delayed fluorescence in living cells.

PubMed

Scholz, Marek; Dědic, Roman; Hála, Jan

2017-11-08

Singlet oxygen is a highly reactive species which is involved in a number of processes, including photodynamic therapy of cancer. Its very weak near-infrared emission makes imaging of singlet oxygen in biological systems a long-term challenge. We address this challenge by introducing Singlet Oxygen Feedback Delayed Fluorescence (SOFDF) as a novel modality for semi-direct microscopic time-resolved wide-field imaging of singlet oxygen in biological systems. SOFDF has been investigated in individual fibroblast cells incubated with a well-known photosensitizer aluminium phthalocyanine tetrasulfonate. The SOFDF emission from the cells is several orders of magnitude stronger and much more readily detectable than the very weak near-infrared phosphorescence of singlet oxygen. Moreover, the analysis of SOFDF kinetics enables us to estimate the lifetimes of the involved excited states. Real-time SOFDF images with micrometer spatial resolution and submicrosecond temporal-resolution have been recorded. Interestingly, a steep decrease in the SOFDF intensity after the photodynamically induced release of a photosensitizer from lysosomes has been demonstrated. This effect could be potentially employed as a valuable diagnostic tool for monitoring and dosimetry in photodynamic therapy.

Singlet-triplet energy differences in divalent five membered cyclic conjugated Arduengo-type carbenes XC2HN2M (M = C, Si, Ge, Sn, and Pb; X = F, Cl, Br, and I)

NASA Astrophysics Data System (ADS)

Vessally, Esmail; Dehbandi, Behnam; Ahmadi, Elaheh

2016-09-01

Singlet-triplet energy differences in Arduengo-type carbenes XC2HN2C compared and contrasted with their sila, germa, stana and plumba analogues; at B3LYP/6-311++G** level of theory. Free Gibbs energy differences between triplet (t) and singlet (s) states (Δ G(t-s)) change in the following order: plumbylenes > stannylenes > germylenes > silylenes > carbenes. The singlet states in XC2HN2C are generally more stable when the electron withdrawing groups such as-F was used at β-position. However, the singlet states in XC2N2HM (M = Si, Ge, Sn, and Pb) are generally more stable when the withdrawing groups such as-F was placed. The puckering energy is investigated for each the singlet and triplet states. The DFT calculations found the linear correlation to size of the group 14 divalent element (M), the ∠N-M-N angle, and the Δ(LUMO-HOMO) of XC2HN2M.

Long-lived 1H singlet spin states originating from para-hydrogen in Cs-symmetric molecules stored for minutes in high magnetic fields.

PubMed

Franzoni, María Belén; Buljubasich, Lisandro; Spiess, Hans W; Münnemann, Kerstin

2012-06-27

Nuclear magnetic resonance (NMR) is a very powerful tool in physics, chemistry, and life sciences, although limited by low sensitivity. This problem can be overcome by hyperpolarization techniques dramatically enhancing the NMR signal. However, this approach is restricted to relatively short time scales depending on the nuclear spin-lattice relaxation time T(1) in the range of seconds. This makes long-lived singlet states very useful as a way to extend the hyperpolarization lifetimes. Para-hydrogen induced polarization (PHIP) is particularly suitable, because para-H(2) possesses singlet symmetry. Most PHIP experiments, however, are performed on asymmetric molecules, and the initial singlet state is directly converted to a NMR observable triplet state decaying with T(1), in the order of seconds. We demonstrate that in symmetric molecules, a long-lived singlet state created by PHIP can be stored for several minutes on protons in high magnetic fields. Subsequently, it is converted into observable high nonthermal magnetization by controlled singlet-triplet conversion via level anticrossing.

Intramolecular singlet-singlet energy transfer in antenna-substituted azoalkanes.

PubMed

Pischel, Uwe; Huang, Fang; Nau, Werner M

2004-03-01

Two novel azoalkane bichromophores and related model compounds have been synthesised and photophysically characterised. Dimethylphenylsiloxy (DPSO) or dimethylnaphthylsiloxy (DNSO) serve as aromatic donor groups (antenna) and the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as the acceptor. The UV spectral window of DBO (250-300 nm) allows selective excitation of the donor. Intramolecular singlet-singlet energy transfer to DBO is highly efficient and proceeds with quantum yields of 0.76 with DPSO and 0.99 with DNSO. The photophysical and spectral properties of the bichromophoric systems suggest that energy transfer occurs through diffusional approach of the donor and acceptor within a van der Waals contact at which the exchange mechanism is presumed to dominate. Furthermore, akin to the behaviour of electron-transfer systems in the Marcus inverted region, a rate of energy transfer 2.5 times slower was observed for the system with the more favourable energetics, i.e. singlet-singlet energy transfer from DPSO proceeded slower than from DNSO, although the process is more exergonic for DPSO (-142 kJ mol(-1) for DPSO versus-67 kJ mol(-1) for DNSO).

Donor-Acceptor-Collector Ternary Crystalline Films for Efficient Solid-State Photon Upconversion.

PubMed

Ogawa, Taku; Hosoyamada, Masanori; Yurash, Brett; Nguyen, Thuc-Quyen; Yanai, Nobuhiro; Kimizuka, Nobuo

2018-06-25

It is pivotal to achieve efficient triplet-triplet annihilation based photon upconversion (TTA-UC) in the solid-state for enhancing potentials of renewable energy production devices. However, the UC efficiency of solid materials is largely limited by low fluorescence quantum yields that originate from the aggregation of TTA-UC chromophores, and also by severe back energy transfer from the acceptor singlet state to the singlet state of the triplet donor in the condensed state. In this work, to overcome these issues, we introduce a highly fluorescent singlet energy collector as the third component of donor-doped acceptor crystalline films, in which dual energy migration, i.e., triplet energy migration for TTA-UC and succeeding singlet energy migration for transferring energy to a collector, takes place. To demonstrate this scheme, a highly fluorescent singlet energy collector was added as the third component of donor-doped acceptor crystalline films. An anthracene-based acceptor containing alkyl chains and a carboxylic moiety is mixed with the triplet donor Pt(II) octaethylporphyrin (PtOEP) and the energy collector 2,5,8,11-tetra- tert-butylperylene (TTBP) in solution, and spin-coating of the mixed solution gives acceptor films of nanofibrous crystals homogeneously doped with PtOEP and TTBP. Interestingly, delocalized singlet excitons in acceptor crystals are found to diffuse effectively over the distance of ~37 nm. Thanks to this high diffusivity, only 0.5 mol% of doped TTBP can harvest most of the singlet excitons, which successfully doubles the solid-state fluorescent quantum yield of acceptor/TTBP blend films to 76%. Furthermore, since the donor PtOEP and the collector TTBP are separately isolated in the nanofibrous acceptor crystals, the singlet back energy transfer from the collector to the donor is effectively avoided. Such efficient singlet energy collection and inhibited back energy transfer processes result in a large increase of UC efficiency up to 9.0%, offering rational design principles towards ultimately efficient solid-state upconverters.

Improved Photodynamic Efficacy of Zn(II) Phthalocyanines via Glycerol Substitution

PubMed Central

Chin, Yunni; Lim, Siang Hui; Zorlu, Yunus; Ahsen, Vefa; Kiew, Lik Voon; Chung, Lip Yong; Dumoulin, Fabienne; Lee, Hong Boon

2014-01-01

Phthalocyanines are excellent photosensitizers for photodynamic therapy as they have strong absorbance in the near infra-red region which is most relevant for in vivo activation in deeper tissular regions. However, most phthalocyanines present two major challenges, ie, a strong tendency to aggregate and low water-solubility, limiting their effective usage clinically. In the present study, we evaluated the potential enhancement capability of glycerol substitution on the photodynamic properties of zinc (II) phthalocyanines (ZnPc). Three glycerol substituted ZnPc, 1–3, (tetra peripherally, tetra non-peripherally and mono iodinated tri non-peripherally respectively) were evaluated in terms of their spectroscopic properties, rate of singlet oxygen generation, partition coefficient (log P), intracellular uptake, photo-induced cytotoxicity and vascular occlusion efficiency. Tetrasulfonated ZnPc (ZnPcS4) was included as a reference compound. Here, we showed that 1–3 exhibited 10–100 nm red-shifted absorption peaks with higher molar absorptivity, and at least two-fold greater singlet oxygen generation rates compared to ZnPcS4. Meanwhile, phthalocyanines 1 and 2 showed more hydrophilic log P values than 3 consistent with the number of glycerol attachments but 3 was most readily taken up by cells compared to the rest. Both phthalocyanines 2 and 3 exhibited potent phototoxicity against MCF-7, HCT-116 and HSC-2 cancer cell-lines with IC50 ranging 2.8–3.2 µM and 0.04–0.06 µM respectively, while 1 and ZnPcS4 (up to 100 µM) failed to yield determinable IC50 values. In terms of vascular occlusion efficiency, phthalocyanine 3 showed better effects than 2 by causing total occlusion of vessels with diameter <70 µm of the chorioallantoic membrane. Meanwhile, no detectable vascular occlusion was observed for ZnPcS4 with treatment under similar experimental conditions. These findings provide evidence that glycerol substitution, in particular in structures 2 and 3, is able to improve the photodynamic properties of ZnPc. PMID:24840576

Improved photodynamic efficacy of Zn(II) phthalocyanines via glycerol substitution.

PubMed

Chin, Yunni; Lim, Siang Hui; Zorlu, Yunus; Ahsen, Vefa; Kiew, Lik Voon; Chung, Lip Yong; Dumoulin, Fabienne; Lee, Hong Boon

2014-01-01

Phthalocyanines are excellent photosensitizers for photodynamic therapy as they have strong absorbance in the near infra-red region which is most relevant for in vivo activation in deeper tissular regions. However, most phthalocyanines present two major challenges, ie, a strong tendency to aggregate and low water-solubility, limiting their effective usage clinically. In the present study, we evaluated the potential enhancement capability of glycerol substitution on the photodynamic properties of zinc (II) phthalocyanines (ZnPc). Three glycerol substituted ZnPc, 1-3, (tetra peripherally, tetra non-peripherally and mono iodinated tri non-peripherally respectively) were evaluated in terms of their spectroscopic properties, rate of singlet oxygen generation, partition coefficient (log P), intracellular uptake, photo-induced cytotoxicity and vascular occlusion efficiency. Tetrasulfonated ZnPc (ZnPcS4) was included as a reference compound. Here, we showed that 1-3 exhibited 10-100 nm red-shifted absorption peaks with higher molar absorptivity, and at least two-fold greater singlet oxygen generation rates compared to ZnPcS4. Meanwhile, phthalocyanines 1 and 2 showed more hydrophilic log P values than 3 consistent with the number of glycerol attachments but 3 was most readily taken up by cells compared to the rest. Both phthalocyanines 2 and 3 exhibited potent phototoxicity against MCF-7, HCT-116 and HSC-2 cancer cell-lines with IC50 ranging 2.8-3.2 µM and 0.04-0.06 µM respectively, while 1 and ZnPcS4 (up to 100 µM) failed to yield determinable IC50 values. In terms of vascular occlusion efficiency, phthalocyanine 3 showed better effects than 2 by causing total occlusion of vessels with diameter <70 µm of the chorioallantoic membrane. Meanwhile, no detectable vascular occlusion was observed for ZnPcS4 with treatment under similar experimental conditions. These findings provide evidence that glycerol substitution, in particular in structures 2 and 3, is able to improve the photodynamic properties of ZnPc.

The violaxanthin cycle protects plants from photooxidative damage by more than one mechanism

PubMed Central

Havaux, Michel; Niyogi, Krishna K.

1999-01-01

When light energy absorbed by plants becomes excessive relative to the capacity of photosynthesis, the xanthophyll violaxanthin is reversibly deepoxidized to zeaxanthin (violaxanthin cycle). The protective function of this phenomenon was investigated in a mutant of Arabidopsis thaliana, npq1, that has no functional violaxanthin deepoxidase. Two major consequences of the npq1 mutation are the absence of zeaxanthin formation in strong light and the partial inhibition of the quenching of singlet excited chlorophylls in the photosystem II light-harvesting complexes. Prolonged exposure of whole plants to bright light resulted in a limited photoinhibition of photosystem II in both npq1 and wild-type leaves, although CO2 fixation and the linear electron transport in npq1 plants were reduced substantially. Lipid peroxidation was more pronounced in npq1 compared with the wild type, as measured by chlorophyll thermoluminescence, ethane production, and the total hydroperoxy fatty acids content. Lipid peroxidation was amplified markedly under chilling stress, and photooxidative damage ultimately resulted in leaf bleaching and tissue necrosis in npq1. The npq4 mutant, which possesses a normal violaxanthin cycle but has a limited capacity of quenching singlet excited chlorophylls, was rather tolerant to lipid peroxidation. The double mutant, npq4 npq1, which differs from npq4 only by the absence of the violaxanthin cycle, exhibited an increased susceptibility to photooxidative damage, similar to that of npq1. Our results demonstrate that the violaxanthin cycle specifically protects thylakoid membrane lipids against photooxidation. Part of this protection involves a mechanism other than quenching of singlet excited chlorophylls. PMID:10411949

Photodynamic inactivation of Escherichia coli - Correlation of singlet oxygen kinetics and phototoxicity.

PubMed

Müller, Alexander; Preuß, Annegret; Röder, Beate

2018-01-01

Photodynamic inactivation (PDI) of bacteria may play a major role in facing the challenge of the ever expanding antibiotic resistances. Here we report about the direct correlation of singlet oxygen luminescence kinetics and phototoxicity in E. coli cell suspension under PDI using the widely applied cationic photosensitizer TMPyP. Through direct access to the microenvironment, the time resolved investigation of singlet oxygen luminescence plays a key role in understanding the photosensitization mechanism and inactivation pathway. Using the homemade set-up for highly sensitive time resolved singlet oxygen luminescence detection, we show that the cationic TMPyP is localized predominantly outside the bacterial cells but in their immediate vicinity prior to photodynamic inactivation. Throughout following light exposure, a clear change in singlet oxygen kinetics indicates a redistribution of photosensitizer molecules to at least one additional microenvironment. We found the signal kinetics mirrored in cell viability measurements of equally treated samples from same overnight cultures conducted in parallel: A significant drop in cell viability of the illuminated samples and stationary viability of dark controls. Thus, for the system investigated in this work - a Gram-negative model bacteria and a well-known PS for its PDI - singlet oxygen kinetics correlates with phototoxicity. This finding suggests that it is well possible to evaluate PDI efficiency directly via time resolved singlet oxygen detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Does photodissociation of molecular oxygen from myoglobin and hemoglobin yield singlet oxygen?

PubMed

Lepeshkevich, Sergei V; Stasheuski, Alexander S; Parkhats, Marina V; Galievsky, Victor A; Dzhagarov, Boris M

2013-03-05

Time-resolved luminescence measurements in the near-infrared region indicate that photodissociation of molecular oxygen from myoglobin and hemoglobin does not produce detectable quantities of singlet oxygen. A simple and highly sensitive method of luminescence quantification is developed and used to determine the upper limit for the quantum yield of singlet oxygen production. The proposed method was preliminarily evaluated using model data sets and confirmed with experimental data for aqueous solutions of 5,10,15,20-tetrakis(4-N-methylpyridyl) porphyrin. A general procedure for error estimation is suggested. The method is shown to provide a determination of the integral luminescence intensity in a wide range of values even for kinetics with extremely low signal-to-noise ratio. The present experimental data do not deny the possibility of singlet oxygen generation during the photodissociation of molecular oxygen from myoglobin and hemoglobin. However, the photodissociation is not efficient to yield singlet oxygen escaped from the proteins into the surrounding medium. The upper limits for the quantum yields of singlet oxygen production in the surrounding medium after the photodissociation for oxyhemoglobin and oxymyoglobin do not exceed 3.4×10(-3) and 2.3×10(-3), respectively. On the average, no more than one molecule of singlet oxygen from every hundred photodissociated oxygen molecules can succeed in escaping from the protein matrix. Copyright © 2013 Elsevier B.V. All rights reserved.