Thermal Effects and Structural Changes of Photosynthetic Reaction Centers Characterized by Wide Frequency Band Hydrophone: Effects of Carotenoids and Terbutryn

Photothermal characteristics and light‐induced structural (volume) changes of carotenoid‐containing and noncontaining photosynthetic reaction centers (RCs) were investigated by wide frequency band hydrophone. We found that the presence of carotenoid either does not play considerable role in the light‐induced conformational movements, or these rearrangements are too slow for inducing a photoacoustic (PA) signal. The kinetic component with a few tens of microseconds, exhibited by the carotenoid‐less RCs, appears to be similar to that of triplet state lifetimes, identified by other methods. The binding of terbutryn to the acceptor side is shown to affect the dynamics of the RC. Our results do not confirm large displacements or volume changes induced by the charge movements and by the charge relaxation processes in the RCs in few hundreds of microseconds time scale that accompanies the electron transfer between the primary and secondary electron acceptor quinones.     

On the nature of phase separation of polymer solutions at high extension rates

Experiments with stretching moderately concentrated polymer solutions have been carried out. Model experiments were carried out for poly(acrylonitrile) solutions in dimethyl siloxane. Just the choice of concentrated solutions allowed for a clear demonstration of a demixing effect with the formation of two separate phases—an oriented polymer fiber and solvent drops sitting on its surface. An original experimental device for following all subsequent stages in the demixing process was built. It combined two light beams, one transverse to the fiber and a second directed along (inside) the fiber, the latter played the role of an optical line. This gives a unique opportunity to observe processes occurring inside a fiber. The process of demixing starts from the volume phase separation across the whole cross section of a fiber at some critical deformation and the propagation of the front of demixing along the fiber. Then a solvent cylindrical skin appears which transforms into a system of separate droplets. New experimental data are discussed based on a comparison of the current different points of view on the phenomenon of deformation‐induced phase separation: thermodynamic shift of the equilibrium phase transition temperature, growth of stress‐induced concentration fluctuations in two‐component fluids, and mechanically pressing a solvent out from a polymer network. The general belief is that a rather specific (so‐called “beads‐on‐a‐string”) structure of a filament is realized in stretching dilute solutions: beads of a polymer solution connected by oriented polymer bridges forming a single object. The situation in stretching moderately concentrated solutions appears quite different: real phase separation was observed. So, the alternative phenomenon to the formation of the “beads‐on‐a‐string” structure has been experimentally proven. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 559–565     

Density functional calculations of NMR shielding tensors for paramagnetic systems with arbitrary spin multiplicity: validation on 3d metallocenes

The calculation of nuclear shieldings for paramagnetic molecules has been implemented in the ReSpect program, which allows the use of modern density functional methods with accurate treatments of spin-orbit effects for all relevant terms up to order Omicron(alpha4) in the fine structure constant. Compared to previous implementations, the methodology has been extended to compounds of arbitrary spin multiplicity. Effects of zero-field splittings in high-spin systems are approximately accounted for. Validation of the new implementation is carried out for the 13C and 1H NMR signal shifts of the 3d metallocenes 4VCp2, 3CrCp2, 2MnCp2, 6MnCp2, 2CoCp2, and 3NiCp2. Zero-field splitting effects on isotropic shifts tend to be small or negligible. Agreement with experimental isotropic shifts is already good with the BP86 gradient-corrected functional and is further improved by admixture of Hartree-Fock exchange in hybrid functionals. Decomposition of the shieldings confirms the dominant importance of the Fermi-contact shifts, but contributions from spin-orbit dependent terms are frequently also non-negligible. Agreement with 13C NMR shift tensors from solid-state experiments is of similar quality as for isotropic shifts.     

Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling

By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C_2v, has been investigated. Four complexes have the general formula [Ni(bpy)X₂]ⁿ⁺ (bpy=2,2′‐bipyridine; X₂=bpy ( 1 ), (NCS^?)₂ ( 2 ), C₂O₄^2? ( 3 ), NO₃^? ( 4 )). In the fifth complex, [Ni(HIM₂‐py)₂(NO₃)]⁺ ( 5 ; HIM₂‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM₂‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm^?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and g_i) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the e_g‐like orbitals and is due to the difference in the σ‐donor strength of NO₃^? and bpy or HIM₂‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t_2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t_2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model.     

Superhyperfine structure of the EPR spectra of Nd<Superscript>3+</Superscript> and U<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The superhyperfine structure of the EPR spectra of impurity Nd³⁺ and U³⁺ ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals has been observed and discussed. In LiYF₄: Nd (g _| = 1.987, g _⊥ = 2.554) and LiTmF₄: Nd, the superhyperfine structure is observed at the orientation of the external magnetic field B in parallel to the c axis of the crystals and consists of nine components with a splitting of ∼15.4 MHz. In LiYF₄: U (g _| = 1.149, g _⊥ = 2.508) and LiLuF₄: U, the superhyperfine structure is observed at both B | c and B ⊥ c and consists of nine and eleven components, respectively, with a splitting of ∼21.5MHz. It should be noted that the resolution of the superhyperfine structure of the EPR spectrum of LiLuF₄: U³⁺ becomes significantly higher with a deviation from the orientation B ⊥ c.     

Some inverse problems in rheology leading to integral equations

Two inverse problems of the integral type, which are of the general importance to rheology, are discussed. The first of them is the possibility of calculating the molecular weight distribution (MWD) from the flow curve and the second one is the interrelation between creep and relaxation functions. It was shown that the first problem is incorrect and any solution is unstable in respect to minor experimental errors. It means that the general solution of this problem is impossible in principle and only estimations of the width of unimodal MWD can be received from the curvature of the flow curve. The possibility of the correct calculation of the creep function exists in case the relaxation curve being approximated by the sum of exponential members. But the approximation of the relaxation curve within the experimental accuracy is the necessary, but not sufficient condition for the correct solution of this integral inverse problem, because not every mode of approximation leads to the satisfactory prediction of creep function.Delivered as the Courtaulds Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

From dynamic modulus via different relaxation spectra to relaxation and creep functions

The main goal of the paper is to compare predictive power of relaxation spectra found by different methods of calculations. The experimental data were obtained for a new family of propylene random copolymers with 1-pentene as a comonomer. The results of measurements include flow curves, viscoelastic properties, creep curves and rubbery elasticity of copolymer melts. Different relaxation spectra were calculated using independent methods based on different ideas. It lead to various distributions of relaxation times and their “weights”. However, all of them correctly describe the frequency dependencies of dynamic modulus. Besides, calculated spectra were used for finding integral characteristics of viscoelastic behaviour of a material (Newtonian viscosity, the normal stress coefficient, steady-state compliance). In this sense all approaches are equivalent, though it appears impossible to estimate instantaneous modulus. The most crucial arguments in estimating the results of different approaches is calculating the other viscoelastic function and predicting behaviour of a material in various deformation modes. It is the relaxation and creep functions. The results of relaxation curve calculations show that all methods used give rather similar results in the central part of the curves, but the relaxation curves begin to diverge when approaching the high-time (low-frequency) boundary of the relaxation curves. The distributions of retardation times calculated through different approaches also appear very different. Meanwhile, predictions of the creep curves based on these different retardation spectra are rather close to each other and coincide with the experimental points in the wide time range. Relatively slight divergences are observed close to the upper boundary of the experimental window. All these results support the conclusion about a rather free choice of the relaxation time spectrum in fitting experimental data and predicting viscoelastic behaviour of a material in different deformation modes. Received: 15 March 2000 Accepted: 18 September 2000