Function of two β-carotenes near the D1 and D2 proteins in photosystem II dimers

The antenna proteins in photosystem II (PSII) not only promote energy transfer to the photosynthetic reaction center (RC) but provide also an efficient cation sink to re-reduce chlorophyll a if the electron transfer (ET) from the Mn-cluster is inhibited. Using the newest PSII dimer crystal structure (3.0 Å resolution), in which 11 β-carotene molecules (Car) and 14 lipids are visible in the PSII monomer, we calculated the redox potentials (E_m) of one-electron oxidation for all Car (E_m(Car)) by solving the Poisson-Boltzmann equation. In each PSII monomer, the D1 protein harbors a previously unlocated Car (Car_D1) in van der Waals contact with the chlorin ring of Chl_Z(D1). Each Car_D1 in the PSII dimer complex is located in the interface between the D1 and CP47 subunits, together with another four Car of the other PSII monomer and several lipid molecules. The proximity of Car bridging between Car_D1 and plastoquinone/Q_A may imply a direct charge recombination of Car⁺Q_A⁻. The calculated E_m(Car_D1) and E_m(Chl_Z(D1)) are, respectively, 83 and 126 mV higher than E_m(Car_D2) and E_m(Chl_Z(D2)), which could explain why Car_D2⁺ and Chl_Z(D2)⁺ are observed rather than the corresponding Car_D1⁺ and Chl_Z(D1)⁺.     

Accumulation and Dynamics of Cu,Pb, Zn and Mn Elements in Kandelia candel (L.) Druce Mangrove Community of Jiulong River Estuary of Fujian

The accumulation and biocycle of Cu, Pb, Zn and Mn elements were studied in Kandelia candel (L.) Druce mangrove community of Jiulong River Estuary of Fujian. The pool amounts of Cu, Pb, Zn and Mn elements in the forest soil (0～30 cm in depth) were 6.86, 4.23, 25.64 and 134. 67 g · m-2, respectively. The respective element contents ranged from in different parts of the plant, 1.85～6.97, 0.37～3.74, 16.0～25.2 and 140～1405 μg· g-1 of Cu, Pb, Zn and Mn. The pool amounts of elements in standing crop of the community were 87.98, 40. 34, 335.34 and 8006.99 mg · m-2 for Cu, Pb, Zn and Mn respectively. The pool amounts of Cu, Pb, Zn and Mn elements in residues were: 593.06, 49.27, 2450.79 and 43486.70 μg · m-2 respectively. The biocycle of the elements in the community were described as follows: Annual uptake of Cu was 10. 17, Pb 4.32, Zn 49. 14 and Mn 2268. 16 mg · m-2; Annual return of Cu was 2.21, Pb 0.70, Zn 18.63 and Mn 1574.98 mg· m-2; Annual retention of Cu was 7.96, Pb 3.62, Zn 30. 51 and Mn 693.18 mg · m-2. The turnover periods of Cu, Pb, Zn and Mn were 40, 58, 18 and 5 year, respectively. The absorption, utilatizion and cycle coefficients were in the order of Mn〉Zn〉Cu〉Pb.     

Comparative Studies on Mn,Cr and Mo Contained Reconstituent Solutions and Proteins Reconstituted with Partially Metallocluster-deficient MoFe Protein

By treating the reduced MoFe protein from Azotobacter vinelandii with o-phenanthroline and O2, an inactive protein partially deficient in both FeMoco and P-cluster could be obtained. The inactive protein could be reactivated by the reconsfituent solutions of different colours which were prepared from mixture in different proportions of ferric homocitrate, Na2S and dithiothreitol (DTT) with K2CrO4, KMnO4 and Na2MoO4, respectively, the inactive protein could be somewhat reactivated by DTF but not by the other compounds or their mixtures which were deficient in one or two of the above compounds. 99Mo was found in the reconstituted protein of the inactive MoFe protein with a reconstituent solution containing 99Mo. Its measurement of differential perturbed angular correlation indicated that 41% of 99Mo in the reconstituted protein were in a state similar to that of 99Mo in 99MoFe protein from K. pneumoniae. The results showed that the reactivation of the inactive MoFe rotein was mainly based on the restoration of its metallocluster content. It seemed to be reasonable to postulate that Mn- or Cr-containing nitrogenase could be obtained likewise by the reconstitution of the inactive protein with the Mn- or Cr-containing reconstituent solution.     

Anti- and pro-oxidative effects of flavonoids on metal-induced lipid hydroperoxide-dependent lipid peroxidation in cultured hepatocytes loaded with α-linolenic acid

Lipid hydroperoxide (LOOH)–dependent lipid peroxidation was induced in α-linolenic acid (LNA)-loaded hepatocytes by adding Fe, Cu, V, or Cd ions at concentrations from 20 to 500 μM. The effects of structurally related flavonoids at concentrations from 10 to 500 μM on the lipid peroxidation were examined. The results with regard to each flavonoid subclass are as follows: (i) Flavonols such as myricetin, quercetin, fisetin, and kaempferol, but not morin, showed dose-dependent antioxidative activity against metal-induced lipid peroxidation at all metal concentrations. Myricetin, quercetin, and fisetin were the most effective antioxidants, although their efficacies depended on the metal ion. Kaempferol and morin had antioxidative activity equal to the other flavonols in the presence of Cu ions, but were much less effective for the other three metal ions. (ii) Flavones, luteolin, apigenin, and chrysin were antioxidative at low Fe concentrations, but were pro-oxidative at high Fe concentrations. Luteolin exhibited antioxidative activity similar to that of catechol-containing flavonols in the presence of the other three metal ions. Apigenin and chrysin also acted as pro-oxidants with V or with all metal ions, respectively. (iii) Taxifolin, a flavanone, also showed both anti- and prooxidative activity, depending on Fe concentrations, but with other metal showed only antioxidative activity ions. (iv) Epigallocatechin, a flavanol, was antioxidative with all metal ions, and its activity was similar to that of catechol-containing flavonols. The various effects of flavonoids on metal-induced lipid peroxidation in LNA-loaded hepatocytes is discussed with regard to the change in redox potential of flavonoid–metal complexes.     

4-Connected azabicyclo[5.3.0]decane Smac mimetics-Zn2+ chelators as dual action antitumoral agents

Putative dual action compounds (DACs 3a–d) based on azabicyclo[5.3.0]decane (ABD) Smac mimetic scaffolds linked to Zn²⁺-chelating 2,2′-dipicolylamine (DPA) through their 4 position are reported and characterized. Their synthesis, their target affinity (cIAP1 BIR3, Zn²⁺) in cell-free assays, their pro-apoptotic effects, and their cytotoxicity in tumor cells with varying sensitivity to Smac mimetics are described. A limited influence of Zn²⁺ chelation on in vitro activity of DPA-substituted DACs 3a–d was sometimes perceivable, but did not lead to strong cellular synergistic effects. In particular, the linker connecting DPA with the ABD scaffold seems to influence cellular Zn²⁺-chelation, with longer lipophilic linkers/DAC 3c being the optimal choice.     

Effect of five fungicides with different modes of action on cobweb disease (Cladobotryum mycophilum) and mushroom yield

The fungicides chlorothalonil, metrafenone, prochloraz‐Mn, thiabendazole and thiophanate‐methyl were tested in vitro and in vivo for their effect on Cladobotryum mycophilum, the mycoparasite that causes cobweb disease in white button mushroom. In vitro experiments showed that metrafenone (EC₅₀= 0.025 mg L^?1) and prochloraz‐Mn (EC₅₀= 0.045 mg L^?1) were the most effective fungicides for inhibiting the mycelial growth of C. mycophilum. Selectivity indexes of the tested fungicides on both C. mycophilum and Agaricus bisporus indicated that metrafenone was also the most selective fungicide, while chlorothalonil was the most toxic fungicide against A. bisporus mycelium. The in vivo efficacy of fungicides for controlling cobweb was evaluated in three mushroom cropping trials, which were artificially inoculated with C. mycophilum (10⁶ conidia m^?2). Prochloraz‐Mn provided good control, although the surface colonised by cobweb reached 12% by the end of the crop cycles. None of the inoculated cropping trials treated with metrafenone showed any cobweb disease symptoms, and neither were any significant phytotoxic effects on mushroom yield recorded. These results indicated that metrafenone can be used as an alternative to prochloraz‐Mn in the control of cobweb disease.     

Revealing Anisotropic Spinel Formation on Pristine Li‐ and Mn‐Rich Layered Oxide Surface and Its Impact on Cathode Performance

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium‐ion batteries. Through the use of carefully prepared Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ crystal samples with six distinct morphologies, surface transition‐metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth‐profiled core‐level spectroscopy, namely, X‐ray absorption spectroscopy, electron energy loss spectroscopy, and atomic‐resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well‐defined model system of battery materials. The present study reports the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition‐metal reduction. The intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.     

人睾丸前列腺素D合成酶在毕赤氏酵母中的表达、纯化及鉴定

L PGDS是一种双功能蛋白 ,即催化PGD2产生和运输亲脂 疏水分子 .L PGDS主要分布于脑和男性生殖器官 ,并分泌到脑脊液、血清、精液、尿液等体液中 .测定体液中L PGDS的含量可辅助诊断一些神经系统疾病、生殖系统疾病、心血管疾病和肾脏疾病等 .在毕赤氏酵母中表达人睾丸前列腺素D合成酶 ,以利于进一步的生物学功能及临床应用研究 .用PCR的方法从质粒pGEX 2T htL PGDS上扩增出人睾丸L PGDS成熟肽基因编码序列 ,经测序证实后 ,将其插入到质粒pPIC9中 ,构建该基因的酵母表达质粒 .电转化毕赤氏酵母GS1 1 5 ,经甲醇诱导后 ,可实现L PGDS的高效、分泌性表达 .镍离子亲合层析法对表达上清进行纯化 ,SDS PAGE分析证实 ,在 2 7kD处有重组蛋白的表达 ,表达量为 2 7mg L .纯化蛋白可与视黄酸结合 ,使其紫外吸收波谱发生红移