PHOTOREACTIVATION IN THE EXTREME HALOPHILIC ARCHAEBACTERIUM Halobacterium cutirubrum

Abstract— Photoreactivation in the extreme halophilic archaebacterium Halobacterium cutirubrum was studied both in vivo and in vitro. Cells irradiated with ultraviolet (UV)-fluences up to 350 J/m² could be completely photoreactivated, indicating very efficient repair of pyrimidine dimers in UV-irradiated DNA. Dark repair is apparently absent in Halobacterium since liquid holding under non-growth conditions did not influence the survival of UV-irradiated cells, while cells remained completely photoreactivable with no change in the kinetics of photoreactivation. Experiments with Halobacterium isolates of different carotenoid content indicated that carotenoids do not influence either UV-inactivation or photoreactivation. Small differences in the rates of UV-inactivation and photoreactivation could be assigned to the occurrence of gas vesicles. Flash experiments and the temperature dependence of photoreactivation indicated an enzymatical reaction. This was confirmed by in vitro experiments with partially purified photoreactivating enzyme. The in vivo action spectrum of photoreactivation showed a main band in the 400-470 nm region with a maximum at 440 nm. Comparison with action spectra of other microorganisms classified the Halobacterium enzyme as a 8-hydroxy-5-deazaflavin type photoreactivating enzyme.     

金属卟啉催化条件下有机化合物与二氧化碳的电羧化反应Ⅰ. 金属卟啉对苄基氯电羧化催化活性的研究

本文研究了系列金属卟啉对苯基氯(phCH~2Cl)和CO~2电羧化反应的催化活性.用熔点,MS,IR,UV鉴别产物为苯乙酸卟脂,利用高效液相色谱(HPLC)定量分析了羧化产物,选出最佳电羧化电解电位为-1.6v(相对于饱和甘汞电极,vs.SCE,下同). 并对催化活性较高的钴卟啉系列配合物进行了深入研究. 探讨了金属卟啉具有催化活性的原因,认为能形成M(Ⅰ)中间体的金属卟啉配合物.具有较高的催化活性.     

THE SIMULATION AND OPTIMIZATION OF GRADIENT ELUTION HPLC

The movement of a particular component along an HPLC column is studied on the ba-sis of equilibrium equations. Numerical simulation of multi--step gradient elution HPLC isperformed by means o? a personal computer program. The location x, as a fraction of thecolumn length, for a given time t o? each compound is calculated, the velocity and corre-sponding acceleration are given as well. Diagrams for x,dx/dt and d~2x/dt~2 versus t display themovement process of the different components along the HPLC column during gradient elu-tion. The prediction of the retention time and peak width, and the optimization for the multi-step gradient elution HPLC are all based on such simulation and the molecular structure ofthe. components is separated as well.     

用倒相换能器抑制声表面波谐振滤波器的直达讯号

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The coherent scattering function of the reptation model: Simulations compared to theory

We present results of Monte Carlo simulations measuring the coherent structure function of a chain moving through an ordered lattice of fixed topological obstacles. Our computer experiments use chains up to 320 beads and cover a large range of wave vectors and a time range exceeding the reptation time. For additional information we also measured the coherent structure function of internal pieces of the chain. We compare our results i) to the predictions of the primitive chain model, ii) to an approximate form resulting from Rouse motion in a coiled tube, and iii) to our recent evaluation of the full reptation model. i) The primitive chain model can fit the data for times , where T ₂ is the Rouse time of the chain. Besides some phenomenological amplitude factor this fit involves the reptation time T ₃ as a second fit parameter. For the chain lengths measured, the asymptotic behavior is not attained. ii) The model of Rouse motion in a tube, which we have criticized before on theoretical grounds, is shown to fail also on the purely phenomenological level. iii) Our evaluation of the full reptation model yields an excellent fit to the data for both total chains and internal pieces and for all wave vectors and all times, provided specific micro-structure effects of the MC dynamics are negligible. Such micro-structure effects show up for wave vectors of the order of the inverse segment size and enforce the introduction of some phenomenological, wave-vector-dependent prefactor. For the dynamics of the total chain our data analysis based on the full reptation model shows the importance of tube length fluctuations. Universal (Rouse-type) internal relaxation, however, is unimportant. It can be observed only in the form of the diffusive motion of a short central subchain in the tube. Finally, we present a fit formula which in a large range of wave vectors and chain lengths reproduces the numerical results of our theory for the scattering from the total chain.Received: 9 July 2003, Published online: 11 November 2003PACS: 83.10.Kn Reptation and tube theories - 82.35.Lr Physical properties of polymers - 83.10.Rs Computer simulation of molecular and particle dynamics     

High-resolution FTIR spectrum of vinyl chloride: rovibrational analysis of the v 10 and v 11 fundamental bands

The Fourier transform gas-phase infrared spectra of the v ₁₀ and v ₁₁ bands of natural CH₂=CHCl have been measured with a resolution of 0.005 cm^?1 in the frequency range 820–1010 cm^?1. These vibrations of symmetry species A″ give rise to c-type bands and the transitions observed are characterized by δK _a = ±1 and δK _c = 0, ±2. Both J and K structures have been resolved in different subbranches and about 1800 (J ≤ 64, K _a ≤ 13) and 2800 (J ≤ 72, K _a ≤ 14) transitions for the v ₁₀ and v ₁₁ fundamentals, respectively, have been identified for the ³⁵Cl isotopomer. Combined analysis of the assigned data with the available ground state constants allowed the determination of the band origins, rotational and centrifugal distortion parameters for the v ₁₀ = 1 and v ₁₁ = 1 excited states of CH₂=CH³⁵Cl isotopic species. The molecular constants obtained account for slight perturbations in the v ₁₀ vibrational level.     

Dynamics on reactive potential energy surfaces: hyperspherical view and signatures of ‘quantum chaos’

Adiabatic energy levels for two prototypical reactions, F + H₂ → HF + H and He + H⁺ ₂ → HeH⁺ + H, are analysed by means of statistical tests. These levels result from quantum mechanical calculations of dynamics based on the hyperspherical approach, and are given as a function of the total inertia of the system measured by the hyperradius ρ The nearest neighbour level spacing distributions of Brody and of Berry and Robnik, the spectral rigidity δ₃ of Dyson and Mehta and the correlation coefficient are reported, together with other properties, such as variance, skewness and kurtosis of the distributions. Trends are studied as a function of ρ, proposed as a natural control variable. For low ρ, which correspond to the transition state, evidence is found of Wigner-like behaviour, which is interpreted as the signature of quantum chaos. On the passage of the systems through intermediate ρ a mixture of Wigner- and Poisson-like behaviour emerges. The situation for high ρ where reactants and products of the reactions are well separated, is characterized by a tendency towards regular Poisson-like behaviour. A comparison between the two investigated systems shows that the chaotic regime in the transition state region is more pronounced for the He reaction, which proceeds through a deep well and whose dynamics are characterized by a rich resonance pattern.     

Exploring the MRCI method for calculating interaction energies: application to the HeNe potential curve

A multi-reference configuration interaction (MRCI) method is described, which is devised for the calculation of interaction energies of van der Waals complexes and applied to calculating the HeNe potential energy curve. The MRCI calculations make use of a generalized Pople-correction in order to account for the lack of size consistency. The orbital space is partitioned into three subspaces: the first active space (AS1), which contains the strongly occupied orbitals; the second active space (AS2), which contains the main intra-correlating orbitals; and the external space (ES). It is shown that, to keep the error below ± 0.2 K in the excitation scheme and the active orbital space it is sufficient to include only σ-orbitals in AS2 and to use an excitation scheme (labelled Qq-MRCI) that encompasses only up to quadruply excited configurations. The final active orbital space (AS2) turned out to be 2s(He), 2pσ(He), 3s(Ne), 3σ(Ne) and 3dσ(Ne). Other MRCI variants, in which most or all quadruply excited configurations were deleted from the CI expansion (Qt- and Tt-MRCI), were found to be inadequate. Using the Qq-MRCI scheme together with a 197-orbital ‘interaction optimized’ basis set (IO197), the MRCI interaction energy at R = 5.7 _a0 was calculated to be -21.12K. The corresponding values at the MP4 and CCSD(T) levels of theory are -20.06 K and -20.99 K, respectively, indicating that the MP4 method is inappropriate for highly accurate calculations on this system. Fitting the calculated data using a generalized Morse function, including an additional C₆/R⁶ term to account for a correct long-range behaviour of the potential, the MRCI well depth was calculated to be -21.16K at R_eq = 5.73a ₀. The MRCI and CCSD(T) potentials have the same quality and are found to be in good agreement with the Hartree-Fock dispersion (HFD-B) potential of Keil, M., Danielson, L. J., and Dunlop, P. J., 1991, J. Chem. Phys., 94, 296. It is concluded that, for basis IO197, the CCSD(T) method is sufficiently accurate for calculating the HeNe interaction. To recover the small, missing contributions (a few tenths of a Kelvin), MRCI should be used.     

THE PROTONATION OF A RETINYL SCHIFF BASE

The hydrogen bonding-protonation equilibrium for retinyl Schiff base/propionic acid or 3-chloropropionic acid systems was examined by Fourier transform infrared spectroscopy in non polar solutions at temperatures ranging from 25 degrees C to about -150 degrees C. The spectra give evidence for the gradual increase in the degree of protonation as temperature is lowered. The bearing of this on applying low temperature spectroscopic results to physiological conditions in rhodopsin research is discussed.     

Linear dynamical systems with integer constraints

We study properties of dynamic discrete-time linear systemswith the input or the state constrained to have integer components.The reachability of input-constrained systems is investigated,and consistency conditions for state-constrained systems aregiven.