O2 activation by nonheme iron complexes: A monomeric Fe(III)-Oxo complex derived from O2

Iron species with terminal oxo ligands are implicated as key intermediates in several synthetic and biochemical catalytic cycles. However, there is a dearth of structural information regarding these types of complexes because their instability has precluded isolation under ambient conditions. The isolation and structural characterization of an iron(III) complex with a terminal oxo ligand, derived directly from dioxygen (O2), is reported. A stable structure resulted from placing the oxoiron unit within a synthetic cavity lined with hydrogen-bonding groups. The cavity creates a microenvironment around the iron center that aids in regulating O2 activation and stabilizing the oxoiron unit. These cavities share properties with the active sites of metalloproteins, where function is correlated strongly with site structure.     

Raman-assisted crystallography reveals end-on peroxide intermediates in a nonheme iron enzyme

Iron-peroxide intermediates are central in the reaction cycle of many iron-containing biomolecules. We trapped iron(III)-(hydro)peroxo species in crystals of superoxide reductase (SOR), a nonheme mononuclear iron enzyme that scavenges superoxide radicals. X-ray diffraction data at 1.95 angstrom resolution and Raman spectra recorded in crystallo revealed iron-(hydro)peroxo intermediates with the (hydro)peroxo group bound end-on. The dynamic SOR active site promotes the formation of transient hydrogen bond networks, which presumably assist the cleavage of the iron-oxygen bond in order to release the reaction product, hydrogen peroxide.     

CHEMISTRY: Harnessing the Power of Diatomics

When a diatomic molecule is broken up into its constituent atoms, these very energetic atoms provide a large driving force for further reaction. Diatomic molecules often do not undergo productive chemistry, however, because the energy needed to break the diatomic bond is also high. In his Perspective, Thorp discusses the work by MacBeth et al., who have synthesized a nonheme iron complex that reacts with O2 to produce two equivalents of a metal-oxo complex. The complex elegantly mimic the ability of some enzymes to influence metal ion coordination spheres.     

A manganese(IV)/iron(III) cofactor in Chlamydia trachomatis ribonucleotide reductase

In a conventional class I ribonucleotide reductase (RNR), a diiron(II/II) cofactor in the R2 subunit reacts with oxygen to produce a diiron(III/IV) intermediate, which generates a stable tyrosyl radical (Y*). The Y* reversibly oxidizes a cysteine residue in the R1 subunit to a cysteinyl radical (C*), which abstracts the 3'-hydrogen of the substrate to initiate its reduction. The RNR from Chlamydia trachomatis lacks the Y*, and it had been proposed that the diiron(III/IV) complex in R2 directly generates the C* in R1. By enzyme activity measurements and spectroscopic methods, we show that this RNR actually uses a previously unknown stable manganese(IV)/iron(III) cofactor for radical initiation.     

A linear, O-coordinated eta1-CO2 bound to uranium

The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)U(III)] [where (AdArOH)3tacn = 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO2 to yield [((AdArO)3tacn)U(IV)(CO2)], a complex in which the CO(2) ligand is linearly coordinated to the metal through its oxygen atom (eta1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O-C-O bond lengths [1.122 angstroms (A) for the O-C bond adjacent to uranium and 1.277 A for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U(IV)=O=C*-O- <--> U(IV)-OC-O-. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.     

Synthesis, structure, and reactivity of an iron(V) nitride

Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. M??bauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.     

A Redox Fuel Cell That Operates with Methane as Fuel at 120{degrees}C

Platinum black efficiently catalyzes the oxidation of methane by iron(III) to generate carbon dioxide and eight equivalents of iron(II) in solutions of sulfuric acid in water. The rate of oxidation increases over 4 hours to reach approximately 4.83 x 10(-2) moles of iron(II) per gram atom of surface platinum per second. A redox fuel cell was assembled that used this reaction in a liquid reformer to generate soluble reducing equivalents of iron(II) from methane, which was electrochemically oxidized to iron(III) in the cell. A vanadium(V)-(IV)-nitric acid-O(2) redox system catalyzed the electrochemical reduction of O(2). The open-circuit voltage of the cell was 0.48 volt, and the maximum power output of the cell was 8.1 milliwatts per cubic centimeter of graphite felt electrode.     

A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450

Thiolate-ligated oxoiron(IV) centers are postulated to be the key oxidants in the catalytic cycles of oxygen-activating cytochrome P450 and related enzymes. Despite considerable synthetic efforts, chemists have not succeeded in preparing an appropriate model complex. Here we report the synthesis and spectroscopic characterization of [FeIV(O)(TMCS)]+ where TMCS is a pentadentate ligand that provides a square pyramidal N4(SR)apical, where SR is thiolate, ligand environment about the iron center, which is similar to that of cytochrome P450. The rigidity of the ligand framework stabilizes the thiolate in an oxidizing environment. Reactivity studies suggest that thiolate coordination favors hydrogen-atom abstraction chemistry over oxygen-atom transfer pathways in the presence of reducing substrates.     

Discovery of an unmelted h-chondrite inclusion in an iron meteorite

The link between H chondrites and silicate inclusions in group IIE iron meteorites has long been suspected, but direct evidence for a common parentage has remained elusive. The discovery of an unmelted chondritic inclusion in the Techado iron meteorite sheds light on the genetic relation between these two groups, providing clues on the origin of chondritic materials as inclusions in iron meteorites. It is proposed that the complex IIE iron meteorite breccias formed by collisions with several different bodies, followed by deep burial of metal and silicate fragments in the asteroidal megaregolith.     

超越整函数fu：z→zexp（z＋u）的动力性质

研究了超越整函数ｆｕ（ｚ）＝ｚｅｘｐ（ｚ＋ｕ）（其中ｕ为复参数）的动力学性质：存在一无界正实数序列｛Ｕｎ｝使得Ｊ｛ｆμｎ｝≠Ｄ,同时对Ｆ（ｆｕ）的分支个数及Ｊ（ｆｕ）上淹没点的情况也作了较详细的研究。     

Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia

Sorption of actinides, particularly plutonium, onto submicrometer-sized colloids increases their mobility, but these plutonium colloids are difficult to detect in the far-field. We identified actinides on colloids in the groundwater from the Mayak Production Association, Urals, Russia; at the source, the plutonium activity is approximately 1000 becquerels per liter. Plutonium activities are still 0.16 becquerels per liter at a distance of 3 kilometers, where 70 to 90 mole percent of the plutonium is sorbed onto colloids, confirming that colloids are responsible for the long-distance transport of plutonium. Nano-secondary ion mass spectrometry elemental maps reveal that amorphous iron oxide colloids adsorb Pu(IV) hydroxides or carbonates along with uranium carbonates.     

DNA damage and oxygen radical toxicity

A major portion of the toxicity of hydrogen peroxide in Escherichia coli is attributed to DNA damage mediated by a Fenton reaction that generates active forms of hydroxyl radicals from hydrogen peroxide, DNA-bound iron, and a constant source of reducing equivalents. Kinetic peculiarities of DNA damage production by hydrogen peroxide in vivo can be reproduced by including DNA in an in vitro Fenton reaction system in which iron catalyzes the univalent reduction of hydrogen peroxide by the reduced form of nicotinamide adenine dinucleotide (NADH). To minimize the toxicity of oxygen radicals, the cell utilizes scavengers of these radicals and DNA repair enzymes. On the basis of observations with the model system, it is proposed that the cell may also decrease such toxicity by diminishing available NAD(P)H and by utilizing oxygen itself to scavenge active free radicals into superoxide, which is then destroyed by superoxide dismutase.     

土壤活性有机碳与养分有效性及作物产量的关系

以吉林省德惠市的典型黑土为主要研究对象，分析了2000-2002年不同耕作施肥措施下土壤活性有机碳、速效养分和作物产量的变化规律及其相互关系；探讨了土壤活性有机碳在土壤肥力中的地位及与其他养分间的关系。结果表明：从2000年起土壤活性有机碳、土壤有效养分和作物产量均呈增加的趋势。土壤活性有机碳的不同类型对土壤养分的有效性贡献不同。易氧化有机碳与碱解氮之间呈极显著的正相关(r0.01=0．403^**,n=48)，而微生物量碳与速效磷间也呈正相关(r0.05=0．312，n=16)。易氧化有机碳与土壤速效钾间呈显著的负相关(r0.05=-0．537^**，n=48)。而微生物量碳与土壤速效钾间呈正相关(r0.05=0．428,n=16)。作物产量与土壤易氧化有机碳呈显著的正相关，与土壤碱解氮、速效磷、速效钾的相关性不显著。     

Inner Core Anisotropy Due to the Magnetic Field--induced Preferred Orientation of Iron

Anisotropy of the inner core of the Earth is proposed to result from the lattice preferred orientation of anisotropic iron crystals during their solidification in the presence of a magnetic field. The resultant seismic anisotropy is related to the geometry of the magnetic field in the core. This hypothesis implies that the observed anisotropy (fast velocity along the rotation axis) indicates a strong toroidal field in the core, which supports a strong field model for the geodynamo if the inner core is made of hexagonal close-packed iron.     

双低油菜数量性状的相关和通径分析

本文应用相关和通径分析的方法对湘油11号,30-53等7个较稳定的双低油菜品系的10个数量性状进行了分析,结果表明:双低油菜遗传相关系数一次有效分枝数,二次有效分枝数、主花序长、主花序有效角果数、单株果数,每果粒数与产量呈极显著正相关。通过通径系数分析,估算出各个因素对产量结果的相对重要性,将其直接效应和间接效应区分开来。     

The Elemental Composition of the Corona of Procyon: Evidence for the Absence of the FIP Effect

The chemical composition of the solar corona is not the same as that of the underlying photosphere. In the corona, elements with a first ionization potential (FIP) of /=10 electron volts (for example, oxygen, neon, and sulfur) by factors of 3 to 10 with respect to the photosphere. The origin of this FIP effect is unknown. The launch of the Extreme Ultraviolet Explorer Satellite (EUVE) opened up the spectroscopic capability required to determine elemental abundances in the coronae of other stars. Spectroscopic observations of the corona of the nearby F5 IV star Procyon obtained with EUVE have yielded estimates of the relative abundances of high- and low-FIP species. The results provide evidence that Procyon, unlike the sun, does not exhibit the FIP effect. Whether the sun or Procyon is more typical of the general late-type stellar population is of fundamental interest to the physics of stellar outer atmospheres and has a bearing on the origin of cosmic rays.     

复方特比萘芬纳米乳的制备及其含量测定

【目的】研制复方特比萘芬纳米乳,并对其含量进行测定。【方法】以特比萘芬、丁香酚和红霉素为供试药物,通过绘制伪三元相图筛选复方特比萘芬纳米乳处方,利用透射电子显微镜(TEM)、Nicomp 388/Zeta PALS激光粒度测定仪分别考察其形态和粒径,采用染色法鉴别纳米乳的类型,利用高效液相色谱法对其含量测定方法进行研究。【结果】复方特比萘芬纳米乳最佳配方中各组分的质量分数分别为：特比萘芬1.3%,丁香酚2.5%,红霉素1.3%,吐温-80 24%,无水乙醇12%,肉豆蔻酸异丙酯2%,蒸馏水56.9%。透射电镜下,复方特比萘芬纳米乳呈圆球形,无粘连;其平均粒径(Z-Average)为11.9 nm,多分散系数(PDI)为0.06。另外还建立了精确测定复方特比萘芬纳米乳3种主药含量的高效液相色谱法。【结论】复方特比萘芬纳米乳制备工艺简单,稳定性良好且质量可控,有望应用于宠物临床。     

Epinephrine reduction of heme: implication for understanding the transmission of an agonist stimulus

Alpha-adrenergic agonists that promote platelet aggregation were found to reduce ferric heme to ferrous heme. Agents that bind iron in heme inhibited epinephrine-induced platelet aggregation. It is proposed that epinephrine first binds to its receptor and then reduces an adjacent heme group to transmit its agonist stimulus.     

Nitrogenase MoFe-protein at 1.16 A resolution: a central ligand in the FeMo-cofactor

A high-resolution crystallographic analysis of the nitrogenase MoFe-protein reveals a previously unrecognized ligand coordinated to six iron atoms in the center of the catalytically essential FeMo-cofactor. The electron density for this ligand is masked in structures with resolutions lower than 1.55 angstroms, owing to Fourier series termination ripples from the surrounding iron and sulfur atoms in the cofactor. The central atom completes an approximate tetrahedral coordination for the six iron atoms, instead of the trigonal coordination proposed on the basis of lower resolution structures. The crystallographic refinement at 1.16 angstrom resolution is consistent with this newly detected component being a light element, most plausibly nitrogen. The presence of a nitrogen atom in the cofactor would have important implications for the mechanism of dinitrogen reduction by nitrogenase.     

Iron isotope constraints on the Archean and Paleoproterozoic ocean redox state

The response of the ocean redox state to the rise of atmospheric oxygen about 2.3 billion years ago (Ga) is a matter of controversy. Here we provide iron isotope evidence that the change in the ocean iron cycle occurred at the same time as the change in the atmospheric redox state. Variable and negative iron isotope values in pyrites older than about 2.3 Ga suggest that an iron-rich global ocean was strongly affected by the deposition of iron oxides. Between 2.3 and 1.8 Ga, positive iron isotope values of pyrite likely reflect an increase in the precipitation of iron sulfides relative to iron oxides in a redox stratified ocean.