Interpretation of multifrequency transient EPR spectra of the P 700 + A0Q K − state in photosystem I complexes with a sequential correlated radical pair model: Wild type versus A0 mutants

Transient electron paramagnetic resonance (TR-EPR) spectra of the electron-hole pair state P ₇₀₀ ⁺ A₀Q _K ^? in photosystem I are numerically calculated. Parameter variation concerns mainly the exchange integralJ of the precursor spin pair state P ₇₀₀ ⁺ A ₀ ^? Q_K and its lifetime τ. A prominent emissive feature in the high-field region (P ₇₀₀ ⁺ part) of the EPR spectrum turns out to be diminished with increasing lifetime τ of the precursor pair state in the case of positive exchange couplingJ>0 (ferromagnetic type). Correspondingly, the emissive feature becomes more pronounced with increasing lifetime τ in the case of negative exchange couplingJ<0 (antiferromagnetic type). These results can be used to interpret the changes in the pattern observed in TR-EPR spectra comparing wild-type and specific A₀ mutants. The central ligating amino acid residue to the A₀ chlorophyll cofactor is mutated from native methionine (M) to leucine (L) in either the PsaA or the PsaB branch. Changes are observed only for the A-side mutant: M688L(PsaA). They are consistent with the following parameters in the precursor pair P ₇₀₀ ⁺ A ₀ ^? :J≈0.5÷1.0 mT and τ=1.5÷2 ns (as compared to τ～0.05 ns in the wild type).     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

High-frequency EPR approach to the electron spin-polarization effects observed in the photosynthetic reaction centers

Time-resolved high-frequency electron paramagnetic resonance (EPR) spectroscopy was applied to study the structure and dynamics of the electron transfer pathways in the photosynthetic RC proteins. When the spin-polarized EPR spectra are recorded at the high field, the singlet-triplet mixing in the radical pairs becomes faster due to the increase of Zeeman interaction, and a sequential electron transfer polarization model, which includes both the primary and secondary radical pairs, should be considered. Application of the sequential electron transfer polarization model for the interpretation of the bacterial RC proteins with a “slow” electron transfer rate reveals the importance of the protein dynamics. It was shown that the reorganization energy for the electron transfer process between P ₈₆₅ ⁺ H^?Q_A and P ₈₆₅ ⁺ HQ _A ^? , but not the change in the structure of the donor-acceptor complex, is a dominant factor that alters the electron transfer rate. The relaxation data, obtained in the delay after laser flash experiment, have been used to estimate the magnetic interaction in the weakly coupled radical pair. High-frequency spin-polarized EPR spectra allow the quantitative characterization of isotopically labeled quinone exchange in the PS I reaction center proteins.     

Comparison of electron spin polarization of P 870 + Qa a − observed in Zn2+-containing and Fe2+-depleted bacterial reaction centers

Recently, a general model has been developed to explain electron spin polarized (ESP) electron paramagnetic resonance (EPR) signals found in systems where radical pairs are formed sequentially. The photosynthetic bacterial reaction center (RC) is such a system in which we can experimentally vary parameters (lifetime, structure, and magnetic interactions in the sequentially formed radical pairs) that affect ESP development in order to test this model. In Fe²⁺-depleted transfer step from intermediate radical pair, P ₈₇₀ ⁺ Q _a ^? which is produced in an electron transfer step from intermediate radical pair, P ₈₇₀ ⁺ I^?. (P ₈₇₀ ⁺ is the oxidized primary donor, a special pair of bacteriochlorophyll molecules, I^? is the reduced bacteriopheophytin acceptor, and Q _a ^? is the reduced primary quinone acceptor.) The lifetime of P ₈₇₀ ⁺ I^? can be shortened relative to the lifetime of P ₈₇₀ ⁺ I^? in Fe²⁺-depleted RCs by substitution of Zn²⁺. We report the first observation of X-band and Q-band ESP EPR signals due to P ₈₇₀ ⁺ Q^? from bacterial reaction centers that contain Zn²⁺. Comparison of these signals to those observed from Fe²⁺-depleted bacterial reaction centers shows intensity differences and g-factor shifts. The results are discussed in terms of the general sequential radical pair model.     

Alteration of the Axial Met Ligand to Electron Acceptor A0 in Photosystem I: Effect on the Generation of P 700 ·+ A 1 ·− Radical Pairs as Studied by W-band Transient EPR

Photosystem I (PS I) mutants from the cyanobacterium Synechocystis sp. PCC 6803 bearing point mutations to the axial ligands of A_0A (M688N_PsaA) and A_0B (M668N_PsaB) were studied by high-field W-band electron paramagnetic resonance (EPR) spectroscopy. It was found that the EPR observables of PS I from the M668N_PsaB mutant were virtual identical to that of the wild type (WT), and are clearly distinct from the M688N_PsaA mutant. In particular, the P ₇₀₀ ^·+ decay kinetics in the M688N_PsaA mutant is significantly slower than in the WT or the M668N_PsaB mutant. The analysis of the out-of-phase electron–electron dipolar electron spin echo envelope modulation shows that in the M668N_PsaB mutant, the estimated distance of 26.0 ± 0.3 Å agrees well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair measured in the X-ray crystal structure. In the M688N_PsaA mutant, two populations are found with estimated distances of 26.0 ± 0.3 and 25.0 ± 0.3 Å in a ratio of 0.7–0.3, which agree well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair and the 24.6 Å distance for the P ₇₀₀ ^·+ A _1B ^·? radical pair measured in the X-ray crystal structure. The data confirm that under the experimental conditions employed in this work, which involve dark-adapted samples without the pre-reduction of the iron–sulfur clusters, electron transport in cyanobacterial PS I is asymmetrical at 100 K, with the majority of electron transfer taking place through the A-branch of cofactors.     

Electronic color centers in SrF2-Na crystals

It was shown that optical bleaching of M _A ⁺ color centers at 80 K in SrF₂-Na crystals causes the core of an M _A ⁺ -center to transform into the V _a ⁺ Me ⁺ V _a ⁺ configuration, in which all three point defects are arranged diagnonally in the cube cell. Reirradiation of an optically bleached crystal by x-rays generates F _D centers in it: V _a ⁺ Me ⁺ V _a ⁺ + e ^? → V _a ⁰ Me ⁺ V _a ⁺ ≡ F _D. The F _D → M _A ⁺ transformation in SrF₂-Na crystals proceeds at T = 135 K, in contrast to the F _A → M _A ⁺ transformations, which take place at T > 200 K.     

Mechanism by which a single water molecule affects primary charge separation kinetics in a bacterial photosynthetic reaction center of Rhodobacter sphaeroides

Using quantum-chemical methods, we have studied the role played by water molecules W-A and W-B that are bound by hydrogen bonds to accessory bacteriochlorophyll molecules B _A and B _B in the process of primary charge separation in the reaction center of Rhodobacter Sphaeroides. We have found that the occurrence of a rotational mode of the W-A molecule at 32 cm^?1 and/or its harmonics in stimulated emission of an electron donor P* and the dynamics of population of the states P⁺B _A ^? and P⁺H _A ^? may be related to the structural heterogeneity of the reaction center and the existence of a conformation in which the W-A molecule is predominantly involved in one hydrogen bond (with BA). Based on the calculated redox potentials B _A and P, it has been shown that the appearance of the W-A molecule in the reaction center reduces the energy of the P⁺B _A ^? state by ??600 cm^?1. This is somewhat smaller than the influence of the amino-acid residue Tyr^M210 (??870 cm^?1) and correlates well with a substantial decrease in the electron transfer rate in mutant forms of reaction centers GM203L (which do not contain W-A molecules) and YM210F (in which Tyr^M210 is replaced with Phe). The data obtained allow us to suggest that rotation of the water molecule with a fixed position of its H atom that is involved in a hydrogen bond with the keto carbonyl group of B _A is initiated due to the charge separation between the halves of special pair P and the formation of the state P _A ⁺ P _B ^? . The large effect of this rotation on the kinetics of population of the states P⁺B _A ^? and P⁺H _A ^? after the excitation of P is quite consistent with its influence on the energy of the state P⁺B _A ^? .     

Structural analysis of three-spin systems of photosystem II by PELDOR

The pulsed electron electron double resonance (PELDOR) pulse sequence is applied to a three-spin system consisting of three radicals (Y _D ^· , Y _Z ^· and Q _A ^? ) generated in spinach PS II. The distance between Y_Z and Q_A has been determined to be 3.4 nm with the previously derived distances of the other radical pairs, 2.9 nm for Y _D ^· -Y _Z ^· and 3.9 nm for Y _D ^· -Q _A ^? . This distance has been derived from the Y _Z ^· -Q _A ^? radical pair trapped in Y_D-less mutants ofChlamydomonas reinhardtii. Furthermore the method was applied to the Y _D ^· -Q _A ^? -Chl _Z ⁺ system to find the unknown distance between Q_A and Chl_Z. The derived distance was 3.4 nm. A triangular configuration was found in the membrane system that gives the relative positions of the electron transfer components.     

Transient and pulsed EPR spectroscopy on the radical pair state P 865 +. Q A −. to study light-induced changes in bacterial reaction centers

The radical pair state P ₈₆₅ ^+. Q _A ^?. (P₈₆₅: primary donor, Q_A: quinone acceptor) in Zn-substituted bacterial reaction centers is investigated using transient and pulsed EPR spectroscopy. For photoexcited samples not frozen in the dark but under continuous illumination, a prolonged lifetime of this radical pair state is observed in agreement with previous studies using time resolved optical spectroscopy. The transient EPR spectra revealed neither a different orientation of the quinone acceptor anion nor a change of itsg-anisotropy in the sample frozen in the charge separated state as compared with that frozen in the dark. The latter finding indicates a similar hydrogen bonding situation for Q _A ^?. in both samples. Changes observed in the transient EPR spectra are interpreted as result of contributions from spin-polarized Q _A ^?. which was generated in part of the sample while freezing under illumination. From the out-of-phase echo modulation pattern observed in the pulsed EPR measurements, it follows that the distance between P ₈₆₅ ^+. and Q _A ^?. is the same in dark frozen samples and in those frozen under continuous illuminaton. This is in contrast to the model suggested by Kleinfeld D., Okamura M.Y., Feher G.: Biochemistry23, 5780 (1984), in which an increased distance and a larger distribution of distances was suggested for samples frozen under illumination. The prolonged lifetime of the radical pair P ₈₆₅ ^+. Q _A ^?. is discussed in terms of differences in the relaxation behaviour of the protein.     

The decay of the Bethe-Salpeter kernel inP(ϕ)2 quantum field models

We extend methods of high temperature expansions to show that for even weakly coupledP(?)₂ quantum field models the Bethe-Salpeter kernel has 4 particle decay. More precisely ifK denotes the Euclidean Bethe-Salpeter kernel $$|K(x_1 ,x_2 ,x_3 ,x_4 )| \leqq Oe^{ - m_0 (1 - \varepsilon )d_2 } ,$$ wherex=(x ⁰,x ¹),d ₂=2|x ₁ ⁰ +x ₂ ⁰ ?x ₃ ⁰ ?x ₄ ⁰ |+|x ₁ ⁰ ?x ₂ ⁰ |+|x ₃ ⁰ ?x ₄ ⁰ | and ε(λ)→0 as λ→0. Our methods apply to otherr particle irreducible kernels.     

Theoretical investigation of Q A −· -ligand interactions in bacterial reaction centers ofRhodobacter sphaeroides

Density functional theory was used to calculate magnetic resonance parameters for the primary stable electron acceptor anion radical (Q _A ^?· ) in its binding site in the bacterial reaction center (bRC) ofRhodobacter sphaeroides. The models used for the calculations of the Q _A ^?· binding pocket included all short-range interactions of the ubiquinone with the protein surroundings in a gradual manner and thus allowed a decomposition and detailed analysis of the different specific interactions. Comparison of the obtained hyperfine and quadrupole couplings with experimental data demonstrates the feasibility and reliability of calculations on such complex biologically relevant systems. With these results, the interpretation of previously published 3-pulse electron spin echo envelope modulation data could be extended and an assignment of the observed double quantum peak to a specific amino acid is proposed. The computations provide evidence for a slightly altered binding site geometry for the Q_A ground state as investigated by X-ray crystallography with respect to the Q _A ^t-· anion radical state as accessible via EPR spectroscopy. This new geometry leads to improved fits of the W-band correlated-coupled radical pair spectra of Q _A ^?· -P ₈₆₅ ^+· compared to orientation data from the crystal structure. Finally, a correlation of the¹⁴N quadrupole parameters of His219 with the hydrogen bond geometry and a comparison with previous systematic studies on the influence of hydrogen bond geometry on quadrupole coupling parameters (J. Fritscher: Phys. Chem. Chem. Phys. 6, 4950–4956, 2004) is presented.     

Leading/nonleading charm-production asymmetry in Σ− p interactions

The asymmetry between the spectra of leading and nonleading charmed mesons that was measured in Σ^? A interactions at p _L=340 GeV/c in the WA89 experiment is described within the Model of Quark-Gluon Strings (QGS model also known as QGSM) under the assumption that there is a fraction of charmed sea quark-antiquark pairs (intrinsic charm) in an interacting hyperon. It is shown that the asymmetries between D ^?-and D ⁺-meson spectra and between D _s ^? -and D _s ⁺ -meson spectra can be approximated by QGSM curves obtained with the same string-fragmentation parameter, a ₁=10, and the same intrinsic-charm fraction, $\delta _{c,\bar c} = 0.01$ , as those that were used in describing D _s ^? /D _s ⁺ -meson asymmetry of π^? A experiments in previous studies. The asymmetry between the spectra of Λ_c and $\bar \Lambda _c $ that was measured in Σ^? A collisions at p _L=600 GeV/c in the E781 experiment is also described within this scheme. The QGSM results are compared with the results of the calculations in the next-to-leading approximation of perturbative QCD that were performed by other authors.     

The magnetic field dependence of the electron spin polarization in consecutive spin correlated radical pairs in type I photosynthetic reaction centres

The magnetic field/microwave frequency dependence of the spin polarized EPR spectra of the sequential spin correlated radical pairs P⁺A^? ₁ and P⁺F^? _x in type I photosynthetic reaction centres is investigated. Experimental data are presented for photosystem (PS) I and reaction centres of heliobacteria at × band (9.7 GHz) and K band (24 GHz). In photosystem I at ambient temperatures the lifetime of A ^? ₁ is ~290 ns and both states are observable by transient EPR. In heliobacteria, electron transfer to F_x occurs within ~600 ps and only the state P⁺F^? _x is observed. The experimental data show a net polarization of P⁺ in the state P⁺F^? _x, which displays a clear dependence on the strength of the external field. The net polarization generated in sequential radical pairs is expected to pass through a maximum as a function of the Zeeman energy when the characteristic time of singlet-triplet mixing is comparable with the lifetime of the precursor. In PS I, the precursor lifetime (290ns) is much longer than the characteristic time of singlet-triplet mixing at × band (9 GHz, 3 kG) and K band (24 GHz, 8 kG). As a result, the observable net polarization decreases with the field strength in this region. In contrast, in heliobacteria, the precursor lifetime (600 ps) is much shorter than the characteristic time of singlet-triplet mixing, and the net polarization increases in the same range of Zeeman energies. The polarization patterns in these two systems can be described using the specific limiting cases of a short lived and long lived precursor radical pair and written as a sum of several contributions. The spectra are simulated on this basis using parameters derived entirely from independent experimental data, and good agreement between the experimental polarization patterns is obtained. The calculated polarization patterns are sensitive to spin dynamics on a timescale much shorter than the spectrometer response time, and the expected influence of a 10 ns component in the electron transfer, as observed optically in some PS I, preparations is discussed. No significant influence from such a component is found in the spin polarization patterns of PS I from the cyanobacterium Synechocystis 6803.     

Investigation of neutral-kaon production in pC,pSi and pPb Collisions at 70 GeV/c

The results obtained by measuring the inclusive distributions of the Feynman variable x _F and the transversemomentum for the production of K _S ⁰ mesons in proton-nucleus interactions at 70 GeV/c for three targets (C, Si, and Pb) are presented. The mass-number (A) dependence of the cross section for K _S ⁰ -meson production is studied. The measured value of the exponent α in the formula σ ～ A ^α agrees within the errors with its counterpart at higher energies. With the aid of the A dependence, the measured yield of K _S ⁰ mesons at x _F = 0 is compared with the yield of K ⁺ and K ^? mesons in the proton-proton reaction at 70 GeV/c. The inclusive spectra of longitudinal and transverse variables for K _S ⁰ -meson production are contrasted against the predictions of the FRITIOF and UrQMD models.     

High-frequency EPR studies on cofactor radicals in photosystem I

Electron paramagnetic resonance (EPR) spectroscopy at W-band (94 GHz) is used to resolve theg-tensors of the radical ions of the primary chlorophyll donor P ₇₀₀ ^+? and the quinone acceptor A ₁ ^?? in photosystem I. The obtainedg-tensor principal values are compared with those of the isolated pigment radicals in organic solvents and the shifts are related to an impact of the protein environment. P ₇₀₀ ^+? has been investigated in photosystem I single crystals at 94 GHz. W-band EPR applied to the photoinduced radical pair P ₇₀₀ ^+? A ₁ ^?? is used to correctly assign theg-tensor axes of P ₇₀₀ ^+? to the molecular structure of the primary donor. Density functional theory calculations on a model of A ₁ ^?? in its binding pocket derived from the recent crystal structure of photosystem I were utilized to correlate experimental magnetic resonance parameters with structural elements of the protein.     

Lebensdauer- und Hyperfeinstrukturmessungen an einigen angeregten Zuständen der Konfiguration 4d 9 5p im Pd I-Spektrum mit der Level-crossing-Methode

Lifetimes and hfs coupling constants of some excited states of the 4d ⁹ 5p configuration of Pd I have been determined in a level crossing experiment by observing the field dependence of the polarization of the fluorescence radiation in a magnetic field. From the halfwidths of the measured zero field level crossing signals one obtains the mean lifetimes of the following fine structure states:τ(³P ₁ ⁰ )=(7.46±0.32)nsec;τ(³ P ₂ ⁰ )=(6.9±0.76)nsecτ(³P ₁ ⁰ )=(4.99±0.35)nsec;τ(³ D ₁ ⁰ )=(4.89±0.40)nsecτ((³D ₃ ⁰ )=(6.99±0.49)nsec;τ(³ F ₄ ⁰ )=(7.09±0.46)nsec.Δm=2 crossing signals were detected in the³ P ₁ ⁰ ,³D ₃ ⁰ and³F ₄ ⁰ -states of the odd isotope¹⁰⁵Pd. A detailed analysis of the experimental curves yields the hfs coupling constantsA andB of these states:A(³P ₁ ⁰ )=?(133±2) Mc/sec;B(³ P ₁ ⁰ )=(140±30) Mc/secA(³D ₃ ⁰ )=?(120±10) Mc/sec;B(³ D ₃ ⁰ )=?(660±100) Mc/secA(³F ₄ ⁰ )=?(87±2) Mc/sec;B(³ F ₄ ⁰ )=?(330±30) Mc/sec. A theoretical calculation of the hfs constants is given on the basis of reduced matrix elements. Within the limit of the errors these values agree with the experimental ones. The nuclear electric quadrupole moment deduced from the measuredB values isQ (¹⁰⁵Pd)=(0.8±0.3)·10^?24 cm² (without corrections).     

Electron paramagnetic resonance and spinlattice relaxation of Cu2+ ions in ZnSeO4·6H2O

In this paper, we present detailed studies of the EPR spectra of Cu²⁺ ions in single crystals of ZnSeO₄·6H₂O. We describe the spectrum with a rhombic spin Hamiltonian with the following parameters: g_z=2.427; g_y=2.095; g_x=2.097; A _z ⁶⁵ =138.4·10^?4 cm^?1; A _x ⁶⁵ =22.3·10^?4 cm^?1. We studied spin-lattice relaxation in the temperature range 4–300 K at the frequency v≈9.3 GHz. The measured spin-lattice relaxation rate for the orientation H∥L₄ is described well at T<5 K by a linear dependence, while at T>5 K it is described by the sum of three exponentials: $$T_1^{ - 1} = 0.27T + 3.3 \cdot 10^{\text{s}} \exp \left( {\frac{{ - 69.5}}{T}} \right) + 2.6 \cdot 10^7 \exp \left( {\frac{{ - 140}}{T}} \right) + 1.36 \cdot 10^{10} \exp \left( {\frac{{ - 735.6}}{T}} \right){\text{ sec}}^{{\text{ - 1}}} $$ .We discuss possible reasons for the exponential dependence of T ₁ ^?1 for the Raman process.     

A simple idea in explaining the baryon production of\bar p p interactions by the quark framework

A simple idea about quark-quark or quark-diquark reaction mechanism is proposed to predict thex _F spectra in \(\bar p\) p interactions. Over a wide energy range, it is applied to the strange particle production in \(\bar p\) interactions and found that it reproduces well thex _F spectra of strange particleK _s ⁰ ,K ^*± ,Ε ⁰ andΣ ⁺(1385) productions, especially, including the leading effect in the case of strange baryonΕ ⁰,Σ ⁺(1385) productions.     

Resonance strengths,branching ratios and mean lifetimes of nuclear energy levels in23Na

The gamma decay of the²²Ne(p, y)²³Na resonances in the proton energy rangeE _p=1.0→2.0 MeV has been investigated with a 20cm³ Ge(Li) detector. Implanted targets were used. The absolute strengths of the strongest resonances were determined and the branching ratios of twenty resonance levels and several bound states are reported. Mean lifetimes of the levels atE _x=2.078 MeV (18.7±3.5 fs), 2.393 MeV (580 _?190 ⁺³⁷⁰ fs), 2.641 MeV (88 _?14 ⁺²⁰ fs), 2.985 MeV (4.0 _?1.0 ^+1.3 fs), 3.679 MeV (24 _?4 ⁺⁵ fs), 3.915 MeV (7.4 _?2.0 ^+2.5 fs) and 4.775 MeV (<2.0 fs) were obtained from measurements of the gamma ray Doppler shifts.     

Two-particle production inK + p interactions at 32 GeV/c

Results are presented on two-particle inclusive production inK ⁺ p interactions at 32 GeV/c. We study thex _1,2=x ₁+x ₂ dependence of invariant structure functions of (ππ)-pairs and compare them to single particle inclusive distributions in the fragmentation regions. Distributions of particles observed at Feynmanx ₂ in association with various “trigger” particles or systems atx ₁ in the same hemisphere are dicussed in terms of the reduced variable \(\tilde x_2 = x_2 /(1 - |x_1 |)\) . We further present absolute production rates and production ratios of π⁺'s and π^?'s associated with π^±,K _s ⁰ , Λ, \(\bar \Lambda \) ,K ^*+ (890), (K _s ⁰ π⁺), and (π⁺ π^?)-triggers, and compare them with qualitative predictions of the quark recombination model. Forwardbackward correlations between (K _s ⁰ π^±), (K _s ⁰ ,p), (Λ, π^?), \((\bar \Lambda \pi ^ \pm )\) , and (p, π^?) pairs are also discussed.