Single-crystal (57)Fe Q-band ENDOR study of the 4 iron-4 sulfur cluster in its reduced [4Fe-4S](1+) state.

(57)Fe Q-band ENDOR has been used to study the [4Fe-4S](1+) state created by gamma irradiation of single crystals of the synthetic model compound [N(C(2)H(5))(4)](2)[Fe(4)S(4)(SCH(2)C(6)H(5))(4)] enriched in (57)Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron-4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe-4S](3+) and reduced [4Fe-4S](1+) paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the (57)Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe-4S](1+) species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two (57)Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.     

含O3MoS3单元的配合物[Mox（CO）y（O,S—C6H4—1,2）3FezLm[^n—（x=1,2或3,y=0,3

用红外光谱研究标题配合物的结构,得到了很有意义的结果。     

Lead-enhanced gas-phase stability of multiply charged EDTA anions: a combined experimental and theoretical study

Besides their fundamental importance, multiply charged anions (MCAs) are considered as promising molecular capacitors for which their intrinsic stabilities are of great significance. Herein, the gas-phase stabilities of ethylenediaminetetraacetic acid (EDTA) anions (i.e. [EDTA-nH](n-), n = 1-4) and their Pb(II) complexes (i.e. [EDTA + Pb-nH]((2-n)-), n = 3, 4) have been investigated using an approach that combines extractive electrospray ionization mass spectrometry (EESI-MS) measurements, Car-Parrinello molecular dynamics simulations and density functional theory/Tao-Perdew-Staroverov-Scuseria calculations. The EESI-MS data showed that the doubly charged EDTA anions in the form of [EDTA-2H](2-) and [EDTA + Pb-4H](2-) were much more abundantly observed than the singly charged species such as [EDTA-H](-) and [EDTA + Pb-3H](-), respectively. The calculation results indicated that [EDTA-2H](2-) and [EDTA + Pb-4H](2-) anions were thermodynamically more stable than the [EDTA-H](-) and [EDTA + Pb-3H](-) species in the gas phase, respectively. The [EDTA + Pb-3H](-) anions preferred five-coordinated structure, whereas [EDTA + Pb-4H](2-) anions formed either five-coordinated or six-coordinated structures. The calculations further revealed that significant electron clouds drifting from the ligand EDTA to the metal Pb(II) ions and the large distances between the carboxylic groups reduced the Coulomb repulsion among the excess electrons of these MCAs. Our data demonstrated that EESI-MS combined with theoretic calculations were able to provide a deep insight into the fundamental behavior of stability of MCAs in the gas phase and, thus, might be useful tools for studying MCAs for potential molecular capacitors.     

Theoretical prediction for the ground state of (10 )H e with the method of analytic continuation in the coupling constant

Using the method of analytic continuation in the coupling constant with a (8)He +n+n model, we investigated the ground state of (10)He. In addition to a solution with the two valence neutrons in p states ( [ p(1/2 )p(1/2 )](0+ )), we obtained a solution with the valence neutrons in s states ( [s( 1/2) s(1/2)](0+) ) as the ground state. Experimentally, such a state has not yet been observed. This newly predicted state of (10)He with the main component of [s( 1/2)s (1/2) ](0+) corresponds to the ground state of (11)Li with a halo structure.     

两种钌配合物皮秒发光动力学过程研究

采用稳态发光光谱、瞬态发光动力学测量等手段,对两种钉配合物[Ru(bpy)3](ClO4)2和[Ru(bpy)2 HPIP](ClO4)2的发光性质进行了研究.稳态发光光谱表明[Ru(bpy)2 HPIP](ClO4)2发光明显偏弱;皮秒瞬态发光动力学测量显示[Ru(bpy)2 HPIP](ClO4)2的激发态弛豫过程...     

11-钨锌三元杂多阴离子层状化合物的合成、表征及催化活性

用离子交换法将具有K egg in结构11-钨锌三元杂多化合物K8[M ZnW11（H2O）O39]（M=Co2＋、N i2＋、Cu2＋、Cd2＋）嵌入到Zn2A l类水滑石中,得到层状化合物：Zn2A l-[M ZnW11（H2O）O39]（M=Co2＋、N i2＋、Cu2＋、Cd2＋）,并用XRD、IR、UV对其进行了表征。结果表明,杂多阴离子进入水滑石层间后,仍保留了其K egg in结构。利用层状化合物催化合成乙酸正丁酯考察其催化活性,结果表明,层状化合物在酯化反应中显示优良的催化性能。     

Peierls–Nabarro model for dislocations in MgSiO3 post-perovskite calculated at 120 GPa from first principles

We present here the first numerical modelling of dislocations in MgSiO₃ post-perovskite at 120?GPa. The dislocation core structures and properties are calculated through the Peierls–Nabarro model using the generalized stacking fault (GSF) results as a starting model. The GSFs are determined from first-principle calculations using the VASP code. Dislocation properties such as planar core spreading and Peierls stresses are determined for the following slip systems: [100](010), [100](001), [100](011), [001](010), [001](110), [001](100), [010](100), [010](001), ½[110](001) and ½[110](110). Our results confirm that the MgSiO₃ post-perovskite is a very anisotropic phase with a plasticity dominated by dislocation glide in the (010) plane.     

Measurements of B decays to two kaons

We report measurements of B meson decays to two kaons using 253 fb(-1) of data collected with the Belle detector at the KEKB energy-asymmetric e+ e- collider. We find evidence for signals in B+ --> K0 K+ and B0 --> K0 K0 with significances of 3.0sigma and 3.5sigma, respectively. (Charge-conjugate modes are included.) The corresponding branching fractions are measured to be [symbol: see text](B+ --> K0 K+) = (1.0 +/- 0.4 +/- 0.1) x 10(-6) and [symbol: see text](B0 --> K0 K0) = (0.8 +/- 0.3 +/- 0.1) x 10(-6). These decay modes are examples of hadronic bd transitions. No signal is observed in the decay B0 --> K+ K-, and we set an upper limit of 3.7 x 10(-7) at 90% confidence level.     

Search for anomalous production of multilepton events in pp collisions at sqrt s=1.96 TeV

We report a search for the anomalous production of events with multiple charged leptons in pp[over] collisions at sqrt[s]=1.96 TeV using a data sample corresponding to an integrated luminosity of 346 pb(-1) collected by the CDF II detector at the Fermilab Tevatron. The search is divided into three-lepton and four-or-more-lepton data samples. We observe six events in the three-lepton sample and zero events in the > or =4-lepton sample. Both numbers of events are consistent with standard model background expectations. Within the framework of an R-parity-violating supergravity model, the results are interpreted as mass limits on the lightest neutralino (chi[over](1)(0)) and chargino (chi[over](1+/-) particles. For one particular choice of model parameters, the limits are M(chi[over](1)(0)>110 GeV/c2 and M(chi[over](1+/-)>203 GeV/c2 at 95% confidence level; the variation of these mass limits with model parameters is presented.     

Reconstruction control of magnetic properties during epitaxial growth of ferromagnetic Mn3-deltaGa on Wurtzite GaN(0001)

Binary ferromagnetic Mn(3-delta)Ga (1.2<3-delta< or =1.5) crystalline thin films have been epitaxially grown on wurtzite GaN(0001) surfaces using rf N-plasma molecular beam epitaxy. The film structure is face-centered tetragonal with CuAu type-I (L1(0)) ordering with (111) orientation. The in-plane epitaxial relationship to GaN is nearly ideal with [110](MnGa) parallel[1100](GaN) and [112](MnGa) parallel[1120](GaN). We observe magnetic anisotropy along both the in-plane and out-of-plane directions. The magnetic moments are found to depend on the Mn/(Mn+Ga) flux ratio and can be controlled by observation of the surface reconstruction during growth, which varies from 1x1 to 2x2 with increasing Mn stoichiometry.     

Rotational Property of~(249)Cm in Particle-Triaxial-Rotor Model

We study the rotational energy spectrum and deformation feature of very heavy nucleus 249Cm in the particle-triaxial-rotor model with variable moment of inertia.Such a nucleus is the unique one involving both multiband structure and high spin states and locating very near the superheavy region.By calculating the energy spectrum,we determine the configurations and quadrupole and triaxial deformation parameters β and γ of the nucleus.The calculated results indicate that the high spin band of 249Cm is built upon the ν[620] 12+configuration with deformation parameters β = 0.296 and γ = 7.5 and the bands based on the ν[622] 32+,ν[613] 72+,ν[750] 12 configuration respectively are also the ones with quite large axial deformation but small triaxial deformation.     

High resolution electron microscopy of precipitates in high Co-Ni alloy steel

In the secondary hardening reaction in ultrahigh strength steel of high Co-Ni alloy, the needle-shaped precipitating carbide is the main strengthening phase. Particular attention has been paid to the nucleation, growth and coarsening of the precipitate and its interface with the ferrite matrix. High resolution transmission electron microscopy observations show that when tempered at a low temperature condition of 454 degrees C for 5h, the precipitating carbides begin to nucleate in the form of clusters; at peak hardening tempered at 482 degrees C, the growing carbides are fully coherent with the matrix, exhibit black-white contrast in bright-field images and have their own hexagonal crystalline structure as M(2)C. Coarsening carbides tempered at high temperature lost their coherence and exhibited Moiré fringes. Lattice images directly indicate the crystallographic relationship of M(2)C carbides and ferrite, [100](alpha)//[1101](beta), [100](alpha)//[1120](beta).     

The dynamics and kinematics of the electron transfer reactions of CF[image omitted] with Ar

The electron transfer reactions between CF [image omitted] and Ar have been studied using a position-sensitive coincidence time-of-flight mass spectrometer. The spectra show the formation of CF [image omitted], CF [image omitted] and CF [image omitted] ions, accompanied by Ar+ ions, by dissociative and non-dissociative electron transfer reactions. Analysis of the PSCO data shows that the CF [image omitted] and CF [image omitted] ions are formed by reactions of ground state CF [image omitted](2B2) ions. The CF [image omitted] product is formed in high lying vibrational states of its ground electronic state, just below the dissociation asymptote to [image omitted]. The formation of CF [image omitted] proceeds via a sequential mechanism, involving the population of highly excited vibrational levels of the ground electronic state of CF [image omitted] which dissociate to CF [image omitted](2A1) + F when the CF [image omitted] is well separated from the Ar+ ion. No evidence of complexation is observed. The energy dependence of the experimental yield of the CF+ ion is consistent with it arising from a reaction of an electronic excited state of CF [image omitted], as proposed in a previous study of this collision system. The unimolecular dissociation of the reactant dications is also observed and indicates that these ions are predominantly in their ground (2B2) electronic state. The kinetic energy release of this unimolecular reaction indicates the metastable well of the CF [image omitted](2B2) state is approximately 3 eV deep and also shows that CF [image omitted](2B2) ions well below the barrier to charge separation can dissociate on the time-scale of the experiment. This observation implicates predissociation, possibly via a repulsive dication state, as the mechanism for the unimolecular charge separation of the ground state of CF [image omitted].     

Combining steady-state and dynamic methods for determining absolute signs of hyperfine interactions: pulsed ENDOR Saturation and Recovery (PESTRE)

The underlying causes of asymmetric intensities in Davies pulsed ENDOR spectra that are associated with the signs of the hyperfine interaction are reinvestigated. The intensity variations in these asymmetric ENDOR patterns are best described as shifts in an apparent baseline intensity that occurs dynamically following on-resonance ENDOR transitions. We have developed an extremely straightforward multi-sequence protocol that is capable of giving the sign of the hyperfine interaction by probing a single ENDOR transition, without reference to its partner transition. This technique, Pulsed ENDOR Saturation and Recovery (PESTRE) monitors dynamic shifts in the 'baseline' following measurements at a single RF frequency (single ENDOR peak), rather than observing anomalous ENDOR intensity differences between the two branches of an ENDOR response. These baseline shifts, referred to as dynamic reference levels (DRLs), can be directly tied to the electron-spin manifold from which that ENDOR transition arises. The application of this protocol is demonstrated on (57)Fe ENDOR of a 2Fe-2S ferredoxin. We use the (14)N ENDOR transitions of the S = 3/2[Fe(II)NO](2+) center of the non-heme iron enzyme, anthranilate dioxygenase (AntDO) to examine the details of the relaxation model using PESTRE.     

Electron spin relaxation enhancement measurements of interspin distances in human, porcine, and Rhodobacter electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO)

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a membrane-bound electron transfer protein that links primary flavoprotein dehydrogenases with the main respiratory chain. Human, porcine, and Rhodobacter sphaeroides ETF-QO each contain a single [4Fe-4S](2+,1+) cluster and one equivalent of FAD, which are diamagnetic in the isolated enzyme and become paramagnetic on reduction with the enzymatic electron donor or with dithionite. The anionic flavin semiquinone can be reduced further to diamagnetic hydroquinone. The redox potentials for the three redox couples are so similar that it is not possible to poise the proteins in a state where both the [4Fe-4S](+) cluster and the flavoquinone are fully in the paramagnetic form. Inversion recovery was used to measure the electron spin-lattice relaxation rates for the [4Fe-4S](+) between 8 and 18K and for semiquinone between 25 and 65K. At higher temperatures the spin-lattice relaxation rates for the [4Fe-4S](+) were calculated from the temperature-dependent contributions to the continuous wave linewidths. Although mixtures of the redox states are present, it was possible to analyze the enhancement of the electron spin relaxation of the FAD semiquinone signal due to dipolar interaction with the more rapidly relaxing [4Fe-4S](+) and obtain point-dipole interspin distances of 18.6+/-1A for the three proteins. The point-dipole distances are within experimental uncertainty of the value calculated based on the crystal structure of porcine ETF-QO when spin delocalization is taken into account. The results demonstrate that electron spin relaxation enhancement can be used to measure distances in redox poised proteins even when several redox states are present.     

氦泡在bcc钨中晶界处成核长大的分子动力学模拟

钨(W)是潜在的聚变堆面向等离子体材料.聚变反应中产生的氦(He)不溶于金属W,并在其中易聚集形成He泡,使W基体发生脆化,从而导致W基体的性能发生退化.在前人工作的基础上,本文采用分子动力学研究了He泡在单晶bcc-W中以及bcc-W中∑3[211](110)和∑9[110](411)晶界处He泡形核长大初期的演化过程.结果发现,晶界处He泡的长大机制和单晶W中有所不同.单晶W中He泡通过挤出位错环促进长大.而He泡在∑3[211](110)晶界处的长大机制为:首先挤出并发射少量自间隙W原子,而后挤出1/2⟨111⟩位错线,随后,该位错线会沿晶界面上[111]方向迁移出去;在∑9[110](411)晶界处,He泡在我们的模拟时间尺度范围内没有观察到W自间隙子的发射和位错的挤出.     

Synthesis of benzopyrano[4,3-b](N-arylsulfonyl)indoles and benzopyrano[3,4-b](N-arylsulfonyl)indoles via intramolecular palladium-catalyzed aryl–aryl coupling reaction

A series of benzopyrano[3,4-b](N-arylsulfonyl) indole derivatives and benzopyrano[4,3-b](N-arylsulfonyl) indole derivatives were synthesized from 2- or 3-methylindole via intermolecular S( N )2 reaction and subsequent intramolecular palladium-catalyzed aryl-aryl coupling reaction for the first time. It was suggested that, besides using the Fischer cyclization, benzopyrano[4,3-b]indoles and benzopyrano[3,4-b]indoles could also be prepared via intermolecular S( N )2 reaction and sequential intramolecular palladium-catalyzed coupling reaction.     

Non-kramers ENDOR and ESEEM of the S = 2 ferrous ion of [Fe(II)EDTA](2-)

We report here the first non-Kramers (NK) ESEEM and ENDOR study of a mononuclear NK center, presenting extensive parallel-mode ESEEM and ENDOR measurements on the S(t) = 2 ferrous center of [Fe(II)ethylenediamine-N,N,N',N'-tetraacetato](2-); [Fe(II)EDTA)](2-). The results disclose an anomalous equivalence of the experimental patterns produced by the two techniques. A simple theoretical treatment of the frequency-domain patterns expected for NK-ESEEM and NK-ENDOR rationalizes this correspondence and further suggests that the very observation of NK-ENDOR is the result of an unprecedentedly large hyperfine enhancement effect. The mixed nitrogen-carboxylato oxygen coordination of [Fe(II)EDTA](2-) models that of the protein-bound diiron centers, although with a higher coordination number. Analysis of the NK-ESEEM measurements yields the quadrupole parameters for the (14)N ligands of [Fe(II)EDTA](2-), K = 1.16(1) MHz, 0 相似文献   

钴(Ⅲ)的联吡啶类混配配合物的合成,表征及其与DNA键合的光谱研究

合成了两种新的钴多吡啶类混配配合物。通过元素分析 ,红外 ,紫外 ,核磁方法对其进行表征 ,应用吸收及发射光谱 ,DNA熔点技术 ,循环伏安法 ,研究了其与小牛胸腺DNA的作用。结果显示 ,混配配合物与DNA作用时 ,使紫外吸收明显减色 ,荧光显著增强 ,DNA熔点升高。循环伏安法研究表明 ,配合物仅有还原峰 ,与DNA作用后 ,还原峰电流明显下降。这些结果证明配合物与DNA存在插入结合 ,[Fe(CN) 6 ]4 - 猝灭实验也支持这一结论。峰电位有位移 ,说明配合物与DNA分子中带负电荷的磷酸基团可能存在静电结合 ,进而计算得到配合物与DNA的键合常数分别为 1 8× 10 4 ,4 37× 10 4 。     

Microstructural and compositional characteristics of GaN films grown on a ZnO-buffered Si (111) wafer

Polycrystalline GaN thin films have been deposited epitaxially on a ZnO-buffered (111)-oriented Si substrate by molecular beam epitaxy. The microstructural and compositional characteristics of the films were studied by analytical transmission electron microscopy (TEM). A SiO(2) amorphous layer about 3.5 nm in thickness between the Si/ZnO interface has been identified by means of spatially resolved electron energy loss spectroscopy. Cross-sectional and plan-view TEM investigations reveal (GaN/ZnO/SiO(2)/Si) layers exhibiting definite a crystallographic relationship: [111](Si)//[111](ZnO)//[0001](GaN) along the epitaxy direction. GaN films are polycrystalline with nanoscale grains ( approximately 100 nm in size) grown along [0001] direction with about 20 degrees between the (1l00) planes of adjacent grains. A three-dimensional growth mode for the buffer layer and the film is proposed to explain the formation of the as-grown polycrystalline GaN films and the functionality of the buffer layer.