CHEMICALLY MODIFIED PHOTOSYNTHETIC BACTERIAL REACTION CENTERS: CIRCULAR DICHROISM, RAMAN RESONANCE, LOW TEMPERATURE ABSORPTION, FLUORESCENCE AND ODMR SPECTRA AND POLYPEPTIDE COMPOSITION OF BOROHYDRIDE TREATED REACTION CENTERS FROM Rhodobacter sphaeroides R26

Abstract— Reaction centers from Rhodobacter sphaeroides have been modified by treatment with sodium borohydride similar to the original procedure [Ditson et al., Biochim. Biophys. Acta 766 , 623 (1984)], and investigated spectroscopically and by gel electrophoresis.
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (^TP870).
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm^-1 region, the removed pigment is assigned to Bchl_M, e.g. the "extra" Bchl on the "inactive" M-branch.
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.     

Discrete photopatternable pi-conjugated oligomers for electrochromic devices

Three discrete oligomeric systems including an all-thiophene ( T6) system, a thiophene/phenylene ( TPTTPT) system, and a thiophene/EDOT/phenylene ( TPEEPT) system have been constructed and characterized with emphasis on structural, optical, electrochemical, and spectroelectrochemical properties. For all three chromophores, the radical cation, the dication, and the pi-dimer have been identified and characterized. EPR spectroscopy reveals that the radical cations of TPTTPT and TPEEPT have g values of 2.008-2.012 and peak-to-peak widths in the range 4.2-5.3 G. Formation of the radical cation takes place at a lower potential for TPEEPT than for TPTTPT and T6, whereas subsequent oxidation to the dication occurs more easily for TPTTPT than for TPEEPT and T6. We ascribe this observation to more localized charges in the oxidized species of TPEEPT, which is supported by our finding that the radical cation of TPEEPT is less prone to undergo pi-dimerization than the radical cations of TPTTPT and T6. All the oxidized species are sufficiently stable to allow for optical characterization, and the relative positions of all absorption bands are found to be in agreement with the electrochemical data. For further solid-state modifications of these materials, we have effectively modified the synthetic design and grafted terminal functionalities (e.s. acrylates) onto the discrete oligomers. Of these novel materials, TPEEPT proves to be the most promising anodically coloring material for electrochromics, and it undergoes reversible switching between two different colored states (bright yellow and clear blue) and one almost transparent and color neutral state. Contrast ratios, measured as Delta% T at lambda max, are as high as 62.5%, and switching times are in the range 2-5 s for the coloration process, though significantly longer for the bleaching process. As a proof of concept, we have successfully constructed a simple photopatterned electrochromic device by exploiting the terminal acrylate functionalities of the oligomers in a UV-initiated cross-linking process. To the best of our knowledge, this is the first oligomer-based photopatterned electrochromic device reported in the literature.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

Engineering Escherichia coli for Fermentative Dihydrogen Production: Potential Role of NADH-Ferredoxin Oxidoreductase from the Hydrogenosome of Anaerobic Protozoa

Trichomonas vaginalis generates reduced ferredoxin within a unique subcellular organelle, hydrogenosome that is used as a reductant for H₂ production. Pyruvate ferredoxin oxidoreductase and NADH dehydrogenase (NADH-DH) are the two enzymes catalyzing the production of reduced ferredoxin. The genes encoding the two subunits of NADH-DH were cloned and expressed in Escherichia coli. Kinetic properties of the recombinant heterodimer were similar to that of the native enzyme from the hydrogenosome. The recombinant holoenzyme contained 2.15 non-heme iron and 1.95 acid-labile sulfur atoms per heterodimer. The EPR spectrum of the dithionite-reduced protein revealed a [2Fe–2S] cluster with a rhombic symmetry of g _xyz?=?1.917, 1.951, and 2.009 corresponding to cluster N1a of the respiratory complex I. Based on the Fe content, absorption spectrum, and the EPR spectrum of the purified small subunit, the [2Fe–2S] cluster was located in the small subunit of the holoenzyme. This recombinant NADH-DH oxidized NADH and reduced low redox potential electron carriers, such as viologen dyes as well as Clostridium ferredoxin that can couple to hydrogenase for H₂ production from NADH. These results show that this unique hydrogenosome NADH dehydrogenase with a critical role in H₂ evolution in the hydrogenosome can be produced with near-native properties in E. coli for metabolic engineering of the bacterium towards developing a dark fermentation process for conversion of biomass-derived sugars to H₂ as an energy source.     

High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in axially symmetric coordination complexes

High-frequency and -field electron paramagnetic resonance (HFEPR) has been used to study several complexes of high-spin manganese(III) (3d⁴,S = 2): [Mn(Me₂dbm)X] and [Mn(OEP)X] (X = Cl^?, Br^?), where Me₂dbm^? is the anion of 4,4′-dimethyldibenzoylmethane and OEP^2? is the dianion of 2,3,7,8,12,13,17,18-octaethylporphine. These non-Kramers (integer spin) systems are not EPR-active with conventional magnetic fields and microwave frequencies. However, use of fields up to 15 T in combination with multiple frequencies in the range of 95–550 GHz allows observation of richly detailed EPR spectra. Analysis of the field- and frequency-dependent HFEPR data allows accurate determination of the following spin Hamiltonian parameters for these complexes: [Mn(Me₂dbm)Cl],D = ?2.45(3) cm^?1; [Mn(Me₂dbm)Br],D = ?1.40(2) cm^?1; [Mn(OEP)Cl],D = ?2.40(1) cm^?1; [Mn(OEP)Br],D = ?1.07(1) cm^?1 (E ≈ 0, andg ≈ 2.0 in all cases). Comparison of structural data with the electronic parameters for these and related complexes shows quantitatively the effects of axial and equatorial ligation on the electronic structure of Mn(III). These high-spin complexes can be employed as building blocks in the construction of single-molecule magnets. Thus the accurate determination and understanding of the electronic properties, best obtainable by HFEPR, of these monomeric units is important in understanding and improving the properties of the polynuclear single-molecule magnets which can be formed from them.     

羧甲基纤维素钠水凝胶的制备及其生物降解性研究

用羧甲基纤维素钠(CMC—Na)制得了含水量高达98％的水凝胶，考察了防腐剂、交联剂、无机态氮素、有机态氮素、碳水化合物的加入量以及环境中pH值等因素对生物降解性的影响。结果表明：制备条件不同，水凝胶的生物降解性不同；环境中一定量铵根离子的存在有利于水凝胶的生物降解；在pH=5．2的环境中纤维素酶活性最高，降解程度最大。     

Nitrate radical quantum yield from peroxyacetyl nitrate photolysis

Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is a ubiquitous pollutant that is primarily destroyed by either thermal or photochemical mechanisms. We have investigated the photochemical destruction of PAN using a combination of laser pulsed photolysis and cavity ring-down spectroscopic detection of the NO3 photoproduct. We find that the nitrate radical quantum yield from the 289 nm photolysis of PAN is Phi(NO3)PAN = 0.31 +/- 0.08 (+/-2 sigma). The quantum yield is determined relative to that of dinitrogen pentoxide, which is assumed to be unity, under identical experimental conditions. The instrument design and experimental procedure are discussed as well as auxiliary experiments performed to further characterize the performance of the optical cavity and photolysis system.