Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P⁺B _L ⁻ states (where P is a special pair, B_L is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational h_α mode with frequency 130–150 cm⁻¹ controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P⁺B _L ⁻ is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm⁻¹ for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and B_L and then to bacteriopheophytin H_L. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 294–303, May–June, 2006.     

Observation of signature inversion in odd-odd 178Ir

High spin states in ¹⁷⁸Ir have been studied via the ¹⁵²Sm(³¹P, 5nγ)¹⁷⁸Ir reaction through excitation functions, X-γ and γ-γ-t coincidence measurements. According to the band structure characteristics and the measured intraband B(M1)/B(E2) ratios, two rotational bands are identified and assigned to be associated with the πh _9/2⊗νi _13/2 and πh _11/2⊗νi _13/2 configurations, respectively. Both bands show the signature inversion feature. Received: 23 March 2000 / Accepted: 31 July 2000     

Covalency Measurements via NMR in Lithium Metal Phosphates

³¹P nuclear magnetic resonance (NMR) shifts on the order of thousands of parts per million are observed for olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples, a promising class of Li ion rechargeable battery electrode materials. Variable-temperature ³¹P NMR measurements of shift are used to determine that the supertransferred hyperfine interaction is the dominant mechanism giving rise to these unusually large observed ³¹P shifts. Various models for predicting ³¹P and ⁷Li shifts in LiMPO₄ (M = Mn, Fe, Co, Ni) were investigated. Alloys of LiFe_1−x Mn _x PO₄, where x varies from 0 to 1, were also investigated by ⁷Li NMR. Covalency constants, calculated from variable-temperature NMR shifts and magnetic susceptibility data, are determined for the P–O–M bonds in LiMPO₄ (M = Mn, Fe, Co, Ni) and compared to the covalency constants of the Li–O–M bond. The sign and relative magnitude of the covalency constants are discussed in terms of positive and negative spin densities at the nuclei of interest. The covalency constants for the Li–O–M and P–O–M bonds were measured for Li_1.8Na_0.2FeMn₂(PO₄)₃ and compared to the covalency constants measured in the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. The Li_1.8Na_0.2FeMn₂(PO₄)₃ structure has a volume per transition metal atom and Li–O–M bond distances that are similar to those of the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. Authors' address: Jeffrey A. Reimer, Department of Chemical Engineering, University of California Berkeley, Berkeley, CA 94720, USA     

Yrast bands in N = 91 isotones

The in-beam spectroscopy on N = 91 isotones has been carried out using the ¹²C + ¹⁵⁰Nd reaction. The νi _13/2 and νh _11/2 bands of ¹⁵³Sm have been extended up to 33/2⁺ and 31/2^-, respectively. Two new γ-rays have been located on the top of the unfavored band with νi _13/2 configuration in ¹⁵⁷Dy. Two identical relationships have been established in the low-spin region of the yrast νi _13/2 configuration between ¹⁵³Sm and ¹⁵⁵Gd, and between unfavored bands of ¹⁵⁵Gd and ¹⁵⁷Dy. Here all these nuclei have the same neutron number N = 91. Received: 28 June 2000 / Accepted: 20 October 2000     

Synthesis and Spectral Properties of Novel Fluorescent Poly(oxyethylene Phosphate) Tris(β-diketonate) Europium (III) Complexes

Novel poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes have been synthesized by an improved procedure using the Atherton–Todd reaction conditions. N-ethyldiisopropylamine has been used as a mild base and propylene oxide as an acid scavenger in order to obtain poly(oxyethylene phosphate) in yield and purity higher than those achieved by conventional methods. The compounds have been characterized by ¹H, ¹³C, and ³¹P NMR and FTIR techniques. Their absorption, fluorescent excitation and emission spectra of chloroform and abs. ethanol solutions have been recorded and studied. The luminescent quantum yields and decay times have been determined and a dependence on the length of the oxyethylene spacer between phosphate groups has been established. The new polymer complexes are water soluble and have increased luminescence decay time in comparison with corresponding ternary complexes.     

Weak e+e− lines from internal pair conversion observed in collisions of 238U with heavy nuclei

We present the results of a Doppler-shift correction to the measured e⁺e⁻–sum-energy spectra obtained from e⁺e⁻–coincidence measurements in ²³⁸U +²⁰⁶Pb and ²³⁸U +¹⁸¹Ta collisions at beam energies close to the Coulomb barrier, using an improved experimental setup at the double-Orange spectrometer of GSI. Internal-Pair-Conversion (IPC) e⁺e⁻ pairs from discrete nuclear transitions of a moving emitter have been observed following Coulomb excitation of the 1.844 MeV (E1) transition in ²⁰⁶Pb and neutron transfer to the 1.770 MeV (M1) transition in ²⁰⁷Pb. In the collision system ²³⁸U +¹⁸¹Ta, IPC transitions were observed from the Ta-like as well as from the U-like nuclei. In all systems the Doppler-shift corrected e⁺e⁻–sum-energy spectra show weak lines at the energies expected from the corresponding γ–ray spectra with cross sections being consistent with the measured excitation cross sections of the γ lines and the theoretically predicted IPC coefficients. No other than IPC e⁺e⁻–sum-energy lines were found in the measured spectra. The transfer cross sections show a strong dependence on the distance of closest approach (R_min), thus signaling also a strong dependence on the bombarding energy close to the Coulomb barrier. Received: 22 July 1997 / Revised version: 15 October 1997     

SU(3) coupling schemes for odd-odd nuclei in the interacting boson – fermion – fermion model with both odd proton and odd neutron in natural parity orbits

The SU^BFF(3) dynamical symmetry limits of interacting boson – fermion – fermion model are identified and they are appropriate for heavy deformed odd – odd nuclei for configurations with both the odd proton and odd neutron occupying all the natural parity orbits in the corresponding valence shells. There are three symmetry limits and their correspondence with two quasi-particle (proton-neutron) Nilsson configurations is established; one of the limits mixes both Nilsson n_z's and Λ's and other two limits mix only Nilsson Λ's. The ¹⁹¹Ir (d,t) ¹⁹⁰Ir single nucleon transfer spectroscopic strengths are well described by one of the symmetry limits that mixes only Nilsson Λ's. Received: 22 June 1998     

Correlations in 11B NMR spectra of dihalo derivatives of bis(1,2-dicarbollyl)cobalt(III)

In the ¹¹B NMR spectra of dihalo derivatives of bis(dicarbollyl)cobalt(III), we have identified a correlation between the ¹¹B NMR chemical shifts of substituted boron atoms and boron atoms found in other positions on the carborane skeleton. We have observed an increased shielding effect for fluorine atoms (compared with other halogens), manifested in an upfield shift of the ¹¹B NMR signals for antipodal and trans boron atoms. For the fluorine-containing compound Bu₄N⁺ [8,8′-F₂-3,3′-Co(1,2-C₂B₉H₁₀)₂]⁻, we propose the following sequence of electron density transfer: B(8) → {B(6) and B(10)} → B(4, 7). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 547–549 (cont.), July–August, 2006.     

Dynamic light scattering and <Superscript>31</Superscript>P NMR spectroscopy study of the self-assembly of deoxyguanosine 5'-monophosphate

Self-assembling properties of deoxyguanosine 5'-monophosphate in isotropic solutions of concentrations from 0.5 wt% to 15 wt% were investigated by dynamic light scattering (DLS) and ³¹P NMR spectroscopy. A slow diffusive mode with a diffusion coefficient D _slow∼ 10^-12 m²/s was detected by DLS for the whole concentration range. This mode is assigned to the translational motion of large globular aggregates, similar to those observed in DNA and other polyelectrolyte solutions. The existence of such aggregates was confirmed by freeze fracture electron microscopy. Close to the isotropic-cholesteric phase transition, at 4 wt% c 10 wt%, also a faster diffusive mode is observed in the polarized DLS response and a very fast mode is detected by depolarized DLS. These modes are related to translational and rotational diffusion of the columnar stacks of guanosine molecules, which are favorably formed in the relatively narrow pretransitional region. The stacking was also revealed from the appearance of a secondary resonance line in the ³¹P NMR spectra. Using the hydrodynamic theory of Tirado and Garcia de la Torre, the length of the cylindrical stacks was found to be L = 364±78 ?, which is significantly larger than the values reported for other guanosine derivatives. Received 13 July 2001 and Received in final form 17 October 2001     

Luminescence of praseodymium (III) in solutions of mixed-ligand complexes with β-diketones

We have found that it is possible to enhance the luminescence of Pr(III) in solutions of complexes with β-diketones: acetylacetone derivatives containing fluoroalkyl substituents of different lengths and structures. We have established that in the presence of organic solvents, second (additional) ligands, and surfactants shielding the central ion from the quenching effect of the water molecules (OH oscillators), the intensity of luminescence for Pr(III) increases by a factor of 65, 38, and 45 respectively. In this case, cationic surfactants form ionic associates with Pr(III) β-diketonates, with incorporation of one more β-diketone molecule (ratio Pr:β-diketonate:surfactant = 1:4:1). As a result of suppression of intramolecular energy losses in solutions of Pr(III) β-diketonates, it is possible to observe its rather intense luminescence at 605 nm (the transition ¹D₂ → ³H₄), 612 nm (³P₀ → ³H₆), and 646 nm (³P₀ → 3F₂). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 746–750, November–December, 2006.     

Novel approach to pion and eta production in proton-proton collisions near threshold

We evaluate the threshold matrix–element for the reaction pp→ppπ⁰ in a fully relativistic Feynman diagrammatic approach. We employ a simple effective range approximation to take care of the S–wave pp final–state interaction. The experimental value for the threshold amplitude A = (2.7 −i0.3) fm⁴ can be reproduced by contributions from tree level chiral (long–range) pion exchange and short–range effects related to vector meson exchanges, with ω-exchange giving the largest individual contribution. Pion loop effects appear to be small. We stress that the commonly used heavy baryon formalism is not applicable in the NN–system above the pion production threshold due to the large external momentum, |p|≃ (Mm _π)^−1/2, with M and m _π the nucleon and the pion mass, respectively. We furthermore investigate the reaction pp→pnπ⁺ near threshold within the same approach. We extract from the data the triplet threshold amplitude as B = (2.8 −i1.5) fm⁴. Its real part can be well understood from (relativistic) tree level meson–exchange diagrams. In addition, we investigate the process pp→ppη near threshold. We use a simple factorization ansatz for the ppη final–state interaction and extract from the data the modulus of the threshold amplitude, |C|= 1.32 fm⁴. With g _ηN= 5.3, this value can be reproduced by (relativistic) tree level meson–exchange diagrams and η–rescattering, whose strength is fixed by the ηN scattering length. We also comment on the recent near threshold data for η^′–production. Received: 27 November 1998     

High-spin states in odd-odd 168Lu

High-spin states in the odd-odd ¹⁶⁸Lu nucleus, populated in the ¹⁵⁴Sm(¹⁹F,5n) reaction at a beam energy of 96 MeV, were investigated using in-beam γ-ray spectroscopy techniques. The BC neutron crossing in the yrast band, based on πg _7/2[404]7/2⁺⊗νi _13/2[642]5/2⁺ configuration, occurs at ħω= 0.31 MeV. The two side bands, based on πh _11/2[514]9/2⁻⊗νi _13/2[642]5/2⁺ and πh _9/2[541]1/2⁻⊗νi _13/2[642]5/2⁺ configurations, show anomalous signature-splitting and signature-inversion in the first one, to occur at ħω= 0.24 MeV. A moderately delayed BC-crossing is anticipated in the second one. Received: 15 June 1998 / Revised version: 11 January 1999     

Solid Substrate-Room Temperature Phosphorescence Method for the Determination of Trace Mn(II) Based on Oxidizing Reaction of Hydrogen Peroxide Using α,α′-Bipyridine as Sensitizer

A new solid substrate-room temperature phosphorescence (SS-RTP) method for the determination of trace manganese (II) has been established. It bases on the fact that fullerol (R) emits strong and stable room temperature phosphorescence (RTP) on filter paper substrate. H₂O₂ can oxidize R to cause the SS-RTP quenching. But manganese (II) can obstruct H₂O₂ to oxidize R, and enhance the RTP of R. α,α′-Bipyridine (Bipy) can sensitize the RTP. After adding Bipy, the ΔI _p enhances 7 times than that without Bipy. Under the optimum conditions, the linear dynamic range of this method is 0.016–1.12 pg spot⁻¹ with a detection limit (L.D.) of 4.6 fg spot⁻¹ ( is the absolute mass of Mn²⁺), and the regression equation of working curve is ΔI _p=25.20 + 63.55 (pg spot⁻¹), n=6, r=0.9983. For 0.016 and 1.12 pg spot⁻¹ Mn²⁺, RSDS are 4.3 and 4.8%, respectively (n=7). This method has been applied to the determination of trace manganese (II) in actual sample with high sensitivity and good selection. And the reaction mechanism of SS-RTP is discussed.     

The role of enhanced aromatic -electron donating aptitude of the tyrosyl sidechain with respect to that of phenylalanyl in intramolecular interactions

An exhaustive ab initio and DFT search for energetically stable conformers from the topologically possible set was undertaken on the N-acetyl-phenylalanyl-N-methylamide and N-acetyl-tyrosyl-N-methylamide systems. The geometries of all 81 phenylalanyl and 162 tyrosyl possible rotamers, described under the rules outlined by Multi-Dimensional Conformational Analysis (MDCA), were attempted at each of the RHF/3-21G, RHF/6-31G(d) and B3LYP/6-31G(d) levels of theory. A total of 32 and 66 stable conformational minima were found for the phenylalanyl and tyrosyl amino acid diamides, respectively, at the B3LYP/6-31G(d) level. From the tyrosyl set, 33 unique conformers emerge when the orientation of the A _i ³ dihedral angle (p-OH orientation) is disregarded. A total of 31 conformers were common to both sets and showed nearly identical geometries. The comparison of the optimized DFT geometries of the two systems showed near by perfect linear fits with R² values of 0.9997, 0.9994, 0.9997, and 0.9996 for the φ _i , ψ _i , A _i ¹ , and A _i ² dihedral angles, respectively. Relative energies of the matching 31 conformers also fitted to a linear plot with an R² value of 0.9985. The geometric centroid of the aromatic ring in the sidechain of both systems was found to be within 4.1 ?of the H and O atoms of the peptide groups, in 21 and 2 of the conformers, respectively. None of the non-matching conformers showed any such interaction distance ≤4.1 ?. Received 1st February 2002 / Received in final form 28 May 2002 Published online 13 September 2002     

Determination of the neutron electric form factor from the reaction 3 He(e,e'n) at medium momentum transfer

The electric form factor of the neutron G_En has been determined in double polarized exclusive ³ He(e,e'n) scattering in quasi–elastic kinematics by measuring asymmetries A _⊥, A _∥ of the cross section with respect to helicity reversal of the electron, with the nuclear spin being oriented perpendicular to the momentum transfer q in case of A_⊥ and parallel in case of A_∥. The experiment was performed at the 855 MeV c. w. microtron MAMI at Mainz. The degree of polarization of the electron beam and of the gaseous ³ He target were each about 50%. Scattered electrons and neutrons were detected in coincidence by detector arrays covering large solid angles. Quasi–elastic scattering events were reconstructed from the measured electron scattering angles ϑ_e, φ_e and the neutron momentum vector p _n ^′ in the plane wave impulse approximation. We obtain the result <G _En>_{(0.27 < Q2c2/GeV2 < 0.5)}= 0.0334 ± 0.0033_stat± 0.0028_syst which is averaged over the indicated range of Q ², the squared momentum transfer. This G _En value is significantly smaller than measured from the D(e,e'n) reaction under similar kinematical conditions. To what extent final state interactions in ³He quench the G _En result is subject of calculations currently in progress elsewhere. Received: 29 April 1999     

NMR study of the magnetic properties and electronic structure of amorphous Ni−B−P alloys

The¹¹B and³¹P NMR Knight shift (K) and Korringa spin-lattice relaxation rate (1/T ₁ T) have been measured for amorphous Ni_81.5B_18.5−x P _x alloys with 0≤x≤18.5. In accordance with previous bulk measurements, the³¹P NMR parameters vary markedly with composition whereas the¹¹B NMR parameters remain almost constant except for small P-contents. It is suggested that the d-band contribution toK(³¹P) is positive and that toK(¹¹B) is negative. The data further support our previous conclusion that amorphous Ni_81.5B_18.5 is a Pauli paramagnet rather than a weak itinerant ferromagnet.     

The structure of 99Ru from (α,3n) reaction

The results of in-beam investigations of excited states of ⁹⁹Ru using the ⁹⁸Mo(α,3n) reaction are presented. Angular distributions of γ–rays and γ–γ coincidences have been measured. Excited states have been identified up to an energy of E = 5603 keV and spin of I^π= 31/2⁻. Mean lifetimes τ have been determined using the DSA method for eleven levels. Aligned angular momenta are discussed and the probable (νh _11/2) origin of a backbending at frequency about 0.5 MeV was confirmed. The possible role of (νd _5/2) alignment at frequencies above 0.5 MeV was pointed out. Received: 13 January 1999 / Revised version: 26 March 1999     

Effective nonlinear optical properties of shape distributed composite media

The effective linear and nonlinear optical properties of metal/dielectric composite media, in which ellipsoidal metal inclusions are distributed in shape, are investigated. The shape distribution function P(L _x, L _y) is assumed to be 2Δ^-2θ(L _x - 1/3 + Δ/3)θ(L _y - 1/3 + Δ/3)θ(2/3 + Δ/3 - L _x - L _y), where θ( ^{. . .} ) is the Heaviside function, Δ is the shape variance and L_i are the depolarization factors of the ellipsoidal inclusions along i-symmetric axes (i = x, y). Within the spectral representation, we adopt Maxwell-Garnett type approximation to study the effect of shape variance Δ on the effective nonlinear optical properties. Numerical results show that both the effective linear optical absorption α ∼ ωIm() and the modulus of the effective third-order optical nonlinearity enhancement |χ⁽³⁾ _e|/χ⁽³⁾ ₁ exhibit the nonmonotonic behavior with Δ. Moreover, with increasing Δ, the optical absorption and the nonlinearity enhancement bands become broad, accompanied with the decrease of their peaks. The adjustment of Δ from 0 to 1 allows us to examine the crossover behavior from no separation to large separation between optical absorption and nonlinearity enhancement peaks. As Δ → 0, i.e., the ellipsoidal shape deviates slightly from the spherical one, the dependence of |χ⁽³⁾ _e|/χ⁽³⁾ ₁ on Δ becomes strong first and then weak with increasing the imaginary part of inclusions' dielectric constant. In the dilute limit, the exact formula for the effective optical nonlinearity is derived, and the present approximation characterizes the exact results better than old mean field one does. Received 10 December 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: lgaophys@pub.sz.jsinfo.net     

Nuclear Spin-Lattice Relaxation of 82BrFe

The field dependence of the nuclear spin-lattice relaxation (SLR) of cold implanted ⁸²Br (T ≤ 25 mK) in α-Fe single crystals was investigated with nuclear magnetic resonance of oriented nuclei (NMR/ON) at low temperatures as experimental technique. The SLR at the lattice sites with the hyperfine fields found by earlier NMR/ON experiments was measured as a function of the applied external magnetic field B _ext parallel to the three principle axes [100], [110] and [111] of the iron single crystal. The data were evaluated with the full relaxation formalism in the single impurity limit and for comparison also with the often employed model of a single exponential function with an effective relaxation time T ₁′. With a phenomenological model the high field values of the relaxation rates r _{∞, [100]′} = 6.6(2) · 10⁻¹⁵ T²sK⁻¹, r _{∞, [110]} = 5.4(2) · 10⁻¹⁵ T²sK⁻¹ and r _{∞, [111]} = 5.2(1) · 10⁻¹⁵ T²sK⁻¹ were obtained.     

Influence of additional metal ions on the ratio of the rates of intermediate product transformations in the hydrolysis of adenizine-5′-triphosphoric acid catalyzed by divalent Cu ions

It was shown earlier that the hydrolysis of the (CuATP²⁻)₂ dimeric complex to CuADP⁻ and inorganic phosphate P _i was an irreversible reaction. The main intermediate hydrolysis product, the formation of which should be taken into account at comparatively early hydrolysis stages, was the IntK pentacovalent intermediate. It was formed in parallel with hydrolysis to CuADP⁻ and P _i through the common intermediate product (CuATP²⁻)₂OH⁻ — DOH⁻. We studied the influence of the addition of various concentrations of Mg²⁺ ions to the reaction mixture at pH 7.1–7.2, a range for which the kinetics of hydrolysis is sensitive to the rate constants of deactivation of DOH⁻ active centers (conjugated with CuADP⁻ formation and occurring via the formation of IntK). The conversion of ATP above which stationary hydrolysis regime was observed decreased as the concentration of Mg²⁺ grew. The DOH⁻ $ \underset{{OH^ - }}{\overset{{OH^ - }}{\longleftrightarrow}}$ \underset{{OH^ - }}{\overset{{OH^ - }}{\longleftrightarrow}} IntK equilibrium according to the conversion of ATP was established more rapidly, and it was to a greater extent shifted toward IntK. It was assumed that hydrated Mg²⁺ linked as a second metal ion with ATP β and γ phosphate groups hydrated IntK much stronger than DOH⁻. The Cu · OH₂ · AMP complex played the role of a common acid catalyst and hydrated DOH⁻ better than Mg²⁺ · OH₂. The selective hydration of DOH⁻ by the CuOH₂ · AMP complex at early hydrolysis stages directed the process toward the formation of IntK, which caused the appearance of an induction period in the formation of CuADP⁻.