ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.

A Hierarchical Modeling and Fault Diagnosis Method for Complex Electronic Devices

Due to the shortcomings of the diagnosis systems for complex electronic devices such as failure models hard to build and low fault isolation resolution, a new hierarchical modeling and diagnosis method is proposed based on multisignal model and support vector machine （SVM）. Multisignal model is used to describe the failure propagation relationship in electronic device system, and the most probable failure printed circuit boards （PCBs） can be found by Bayes inference. The exact failure modes in the PCBs can be identified by SVM. The results show the proposed modeling and diagnosis method is effective and suitable for diagnosis for complex electronic devices.

Nonlinear Dynamics in a Nonextensive Complex Plasma with Viscous Electron Fluids

Cylindrical and spherical dust-electron-acoustic （DEA） shock waves and double layers in an unmagnetized, col- lisionless, complex or dusty plasma system are carried out. The plasma system is assumed to be composed of inertial and viscous cold electron fluids, nonextensive distributed hot electrons, Maxwellian ions, and negatively charged stationary dust grains. The standard reductive perturbation technique is used to derive the nonlinear dynamical equations, that is, the nonplanar Burgers equation and the nonplanar further Burgers equation. They are also numerically analyzed to investigate the basic features of shock waves and double layers （DLs）. It is observed that the roles of the viscous cold electron fluids, nonextensivity of hot electrons, and other plasma parameters in this investigation have significantly modified the basic features （such as, polarity, amplitude and width） of the nonplanar DEA shock waves and DLs. It is also observed that the strength of the shock is maximal for the spherical geometry, intermediate for cylindrical geometry, while it is minimal for the planar geometry. The findings of our results obtained from this theoretical investigation may be useful in understanding the nonlinear phenomena associated with the nonplanar DEA waves in both space and laboratory plasmas.

Imaging Ultrafast Plasmon Dynamics within a Complex Dolmen Nanostructure Using Photoemission Electron Microscopy

We report direct nanoscale imaging of ultrafast plasmon in a gold dolmen nanostructure excited with the 7is laser pulses by combining the interferometric time-resolved technology with the three-photon photoemission electron microscopy （PEEM）. The interferometric time-resolved traces show that the plasmon mode beating pattern appears at the ends of the dimer slabs in the dolmen nanostructure as a result of coherent superposition of multiple localized surface plasmon modes induced by broad bandwidth of the ultrafast laser pulses. The PEEM measurement further discloses that in-phase of the oscillation field of two neighbor defects are surprisingly observed, which is attributed to the plasmon coupling between them. Furthermore, the control of the temporal delay between the pump and probe laser pluses could be utilized for manipulation of the near-field distribution. These findings deepen our understanding of ultrafast plasmon dynamics in a complex nanosystem.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS OF NEODYMIUM COMPLEX WITH 8-HYDROXYQUINOLINE AND OCTYLPHENOL POLY(ETHYLENEGLYCOL)ETHER

In this paper the absorption spectra of 4f electron transitions of the neodymlum complex with 8-hydroxyquinoline and octylphenol poly(ethyleneglycol)ether have been studied. The marked intensification of the band at low octylphenol poly(ethyleneglycol)ether concentration is found normally at 575 nm, and its resolution into three sharp bands centering at 572, 580 and 584 nm. The absorbances of the absorption maxima are 3.5 (at 572 nm), 7.2 (at 580 nm) and 10.2 (at 584 nm) times greater than that of the chloride.

Control mechanisms in mitochondrial oxidative phosphorylation

Distribution and activity of mitochondda are key factors in neuronal development, synaptic plasticity and axogenesis. The majority of energy sources, necessary for cellular functions, originate from oxidative phosphorylation located in the inner mitochondrial membrane. The adenosine-5＇- triphosphate production is regulated by many control mechanism-firstly by oxygen, substrate level, adenosine-5＇-diphosphate level, mitochondrial membrane potential, and rate of coupling and proton leak. Recently, these mechanisms have been implemented by ＂second control mechanisms,＂ such as reversible phosphorylation of the tricarboxylic acid cycle enzymes and electron transport chain complexes, aUosteric inhibition of cytochrome c oxidase, thyroid hormones, effects of fatty acids and uncoupling proteins. Impaired function of mitochondria is implicated in many diseases ranging from mitochondrial myopathies to bipolar disorder and schizophrenia. Mitochondrial dysfunctions are usually related to the ability of mitochondria to generate adenosine-5＇-triphosphate in response to energy demands. Large amounts of reactive oxygen species are released by defective mitochondria similarly, decline of antioxidative enzyme activities （e.g. in the elderly） enhances reactive oxygen species production. We reviewed data concerning neuroplasticity, physiology, and control of mitochondrial oxidative phosphorylation and reactive oxygen species production.

An Enzymologic Study on Bone Marrow Cells in Patients with Aplastic Anemia Treated by Supplementing the Kidney and Removing Blood Stasis

The content of cytochrome oxidase (CCO), succinate dehydrogenase (SDH) and neutrophil alkaline phosphatase (NAP) in bone marrow cells in 68 cases of aplastic anemia before and after treatment was determined by computerized graphical analysis and compared with that of normal volunteers (control group). The significantly lowered CCO and SDH levels and the markedly increased NAP content before treatment (P<0.01) became approximately normal after that of supplementing the kidney and removing blood stasis (P >0.05).

Comparative DFT Study of [Mg(CHZ)_3](ClO_4)_2 and [Mg(CHZ)_3](NO_3)_2(CHZ=Carbohydrazide)

The molecular geometry,electronic structure,thermochemistry and infrared spectra of [Mg（CHZ）3]（ClO4）2 and [Mg（CHZ）3]（NO3）2 were comparatively studied using the Heyd-Scuseria-Ernzerhof（HSE） screened hybrid density functional with 6-31G＊＊ basis set.The experimental results show that the complexes have six-coordinated octahedron feature,and the metal-ligand interactions are predominantly ionic in nature.The calculated heats of formation predict that [Mg（CHZ）3]（NO3）2 is more stable than [Mg（CHZ）3]（ClO4）2.Detailed NBO analyses indicate that the ligand-anion interaction plays an important role in the stability for these two energetic complexes.Moreover,the stretching vibration frequencies of N-H bonds shift to lower wave number compared to the free CHZ ligand,which are caused by the delocalizations from N-H bond orbital to lone-pair electron antibond orbital of magnesium.

The Effects of Oxidation States and Spin States of Chromium Interaction with <i>Sargassum Sp</i>.: A Spectroscopic and Density Functional Theoretical Study

The study of various oxidation states of chromium with Sargassum sp. is of particular interest since hexavalent chromium is reduced to trivalent chromium in an aqueous solution. In this study, a systematic density functional theory (DFT) calculations were performed to study the interactions of transition metal chromium ion with different oxidation states and spin states with the Sargassum sp. decorated with carboxylate (acetate) at the wB97XD/6-311++ G(d,p) level of theory. The structures and binding energies of chromium metal-carboxylate complexes at various oxidation states and spin states in gas phase were examined. The coordination strength of Cr(VI) with the acetate ligand was predominantly the strongest compared to the other oxidation states. Vibrational frequency analysis, for the homoleptic monomers of tris [CrIII(AC)3]0 and [CrVI(AC)3]3+ complexes, illustrate good harmony with the experimental and theoretical calculated frequencies. Using the time-dependent DFT (TD-DFT) at the level of CAM-B3LYP/6-311++G(d,p), the vertical excitation energies were obtained. The stabilization energies derived using the second order perturbation theory, Eij(2), of NBO analysis confirmed the greater charge transfer for the observed trends in the metal binding. The calculated binding energies (ΔE) and interactions energies SEij(2) favor the formation of [CrVI(AC)3]3+ complexes. The findings of this study identify efficient electronic factors as major contributors to the metal binding affinities, with promising possibilities for the design of metal-ligand complexes and sensing of the metal ions.

Ab initio studies on the electronic structure of the complexes containing Mo——S bond using relativistic effective core potentials

An ab initio calculation was performed on the electronic structures of MoS,MoS_4^(2-) and Mo_2S_2 using relativistic effective core potential(RECP)for molybdenum,and non-relativistic ECP for sulfur.We predicted that the equilibrium bond length and the dissociation energy of MoS in ground state are 3.89 a.u.and 4.67 eV,respectively,and that the bond is a triple-bond.The ground state of MoS_4^(2-) in Td symmetry is ~1A_1 and π-bonding dominates σ-donation in the molybdenum- sulfur interaction.The Mo_2S_2 is a model contracted from bi-nuclear sulfur-bridged clusters,and the bonding orbitals 1 b_(1u),1b_1g and 1b_2g make the dominant contribution to the stabilization of sulfur- bridged species.

Synthesis of Unprotectedα-Tertiary Amines and 1,2-Amino Alcohols from Vinyl Azides by Light Induced Denitrogenative Alkylarylation/Dialkylation

Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.

Molecular Functions of Oxygen-Evolving Complex Family Proteins in Photosynthetic Electron Flow

Oxygen-evolving complex （OEC） protein is the original name for membrane-peripheral subunits of photosystem （PS） II. Recently, multiple isoforms and homologs for OEC proteins have been iden- tified in the chloroplast thylakoid lumen, indicating that functional diversification has occurred in the OEC family. Gene expression profiles suggest that the Arabidopsis OEC proteins are roughly categorized into three groups： the authentic OEC group, the stressresponsive group, and the group including proteins related to the chloroplast NAD（P）H dehydrogenase （NDH） complex involved in cyclic electron transport around PSI. Based on the above gene expression profiles, molecular functions of the OEC family proteins are discussed together with our current knowledge about their functions.

Investigation on ab initio calculations of the electron donor-acceptor complex H_3N·SiH_3Cl and the hypervalence of Si in it

The formation and the presence of hypervalent Si in the electron donor-acceptor com- plex H_3N·SiH_3 Cl have been investigated by ab initio calculation. The results show that there is a 0.707eV decrease of energy when the complex H_3N.SiH_3 Cl is formed from NH_3 and H_3SiCl, the interaction potential between the donor NH_3 and the acceptor H_3SiCl belongs to the Morse type, and the bond angle A(H-Si-Cl) versus bond length d(N-Si) presents a linear relation. The results also show that the interaction is mainly from giving the lone pair electrons in HOMO of NH_3 to LUMO of H_3SiCl, in which the 2P_z of N and the 3d_0 of Si play important role. Bond N-Si is a weak n-σ*type dative one.

Visible-light-induced N-heterocyclic carbene mediated cascade transformation of N-alkenoxypyridinium salts

While N-alkenoxypyridinium salts are widely used for the synthesis ofα-functionalized ketones via umpolung strategy,such approaches are usually limited to special nucleophiles at high temperatures.Herein,we developed an alternative photoinduced N-heterocyclic carbene(NHC)-mediated functionalization of N-alkenoxypyridinium salts with various nucleophiles,including tetramethylammonium azide,secondary amines,aryl and alkyl thiols,and even the challenging C(sp^(3))-nucleophiles,under mild conditions.A cascade radical-radical coupling/nucleophilic substitution sequence was proposed,wherein the NHC enabled the formation of a photoactive electron donor-acceptor complex forα-iodo ketone synthesis.