Fluxes in "free" and total zinc are essential for progression of intraerythrocytic stages of Plasmodium falciparum

Dynamic fluxes in the concentration of ions and small molecules are fundamental features of cell signaling, differentiation, and development. Similar roles for fluxes in transition metal concentrations are less well established. Here, we show that massive zinc fluxes are essential in the infection cycle of an intracellular eukaryotic parasite. Using single-cell quantitative imaging, we show that growth of the blood-stage Plasmodium falciparum parasite requires acquisition of 30 million zinc atoms per erythrocyte before host cell rupture, corresponding to a 400% increase in total zinc concentration. Zinc accumulates in a freely available form in parasitophorous compartments outside the food vacuole, including mitochondria. Restriction of zinc availability via small molecule treatment causes a drop in mitochondrial membrane potential and severely inhibits parasite growth. Thus, extraordinary zinc acquisition and trafficking are essential for parasite development.     

Resonance Raman studies of the iron(II)--alpha-keto acid chromophore in model and enzyme complexes.

The bidentate coordination of an alpha-keto acid to an iron(II) center via the keto group and the carboxylate gives rise to metal-to-ligand charge-transfer transitions between 400 and 600 nm in model complexes and in alpha-ketoglutarate-dependent dioxygenases. Excitation into these absorption bands of the Fe(II)TauD(alpha-KG) complex (TauD = taurine/alpha-ketoglutarate dioxygenase, alpha-KG = alpha-ketoglutarate) elicits two resonance Raman features at 460 and 1686 cm(-1), both of which are sensitive to (18)O labeling. Corresponding studies of model complexes, the six-coordinate [Fe(II)(6-Me(3)-TPA)(alpha-keto acid)](+) and the five-coordinate [Fe(II)(Tp(Ph2))(alpha-keto acid)] (6-Me(3)-TPA = tris[(6-methyl-2-pyridyl)methyl]amine, Tp(Ph2) = hydrotris(3,5-diphenylpyrazol-1-yl)borate), lead to the assignment of these two features to the Fe(II)(alpha-keto acid) chelate mode and the nu(C==O) of the keto carbonyl group, respectively. Furthermore, the chelate mode is sensitive to the coordination number of the metal center; binding of a sixth ligand to the five-coordinate [Fe(II)(Tp(Ph2))(benzoylformate)] elicits a 9--20 cm(-1) downshift. Thus, the 10 cm(-1) upshift of the chelate mode observed for Fe(II)TauD(alpha-KG) upon the addition of the substrate, taurine, is associated with the conversion of the six-coordinate metal center to a five-coordinate center, as observed for the iron center of clavaminate synthase from X-ray crystallography (Zhang, Z.; et al. Nat. Struct. Biol. 2000, 7, 127-133) and MCD studies (Zhou, J.; et al. J. Am. Chem. Soc. 1998, 120, 13539--13540). These studies provide useful insights into the initial steps of the oxygen activation mechanism of alpha-ketoglutarate-dependent dioxygenases.     

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Axial ligand substituted nonheme FeIV=O complexes: observation of near-UV LMCT bands and Fe=O Raman vibrations

Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.     

Bis(mu-oxo)dimetal "diamond" cores in copper and iron complexes relevant to biocatalysis

Although quite a familiar feature in high-valent manganese chemistry, the M(2)(mu-O)(2) diamond core motif has only recently been found in synthetic complexes for M=Cu or Fe. Structural and spectroscopic characterization of these more reactive Cu(2)(mu-O)(2) and Fe(2)(mu-O)(2) compounds has been possible through use of appropriately designed supporting ligands, low-temperature handling methods, and techniques such as electrospray ionization mass spectrometry and X-ray crystallography with area detector instrumentation for rapid data collection. Despite differences in electronic structures that have been revealed through experimental and theoretical studies, Cu(2)(mu-O)(2) and Fe(2)(mu-O)(2) cores exhibit analogously covalent metal-oxo bonding, remarkably congruent Raman and extended X-ray absorption fine structure (EXAFS) signatures, and similar tendencies to abstract hydrogen atoms from substrates. Core isomerization is another common reaction attribute, although different pathways are traversed; for Fe, bridge-to-terminal oxo migration has been discovered, while for Cu, reversible formation of an O-O bond to yield a peroxo isomer has been identified. Our understanding of biocatalysis has been enhanced significantly through the isolation and comprehensive characterization of the Cu(2)(mu-O)(2) and Fe(2)(mu-O)(2) complexes. In particular, it has led to the development of new mechanistic notions about how non-heme multimetal enzymes, such as methane monooxygenases, fatty acid desaturase, and tyrosinase, may function in the activation of dioxygen to catalyze a diverse array of organic transformations.     

胜利渣油在掺兑物下热反应体系的相态分离行为

本文通过应用显微镜考察掺兑物（供氢剂、溶剂）存在下渣油热反应体系的物理相态 规律，产了热反应体系的相态分离现象。新相态的形成对不同的热反应体系有共同的物理／化学过程，揭示了新的生成对相态分离的依赖性。考察了热处理温度、热处理时间、液相掺兑物、体系的结构／组成对新相态形成特性的影响。     

Steroid profiles determined by capillary electrochromatography, laser-induced fluorescence detection and electrospray-mass spectrometry

Macroporous, monolithic capillary electrochromatography (CEC) columns, featuring a hydrophobic stationary phase, have been applied to the separations of steroids with good column efficiency. Using isocratic and gradient elution runs, mixtures of neutral or conjugated steroids could be resolved. While dansylated ketosteroids were detectable through laser-induced fluorescence at attomole levels, the CEC columns coupled to electrospray-ion-trap mass spectrometry featured femtomole detection limits.