Synthesis, characterization and reactivity studies of electrophilic ruthenium(II) complexes: a study of H-2 activation and labilization

Reaction of 2,2'-bipyridine (bpy) with dinuclear complexesRuCl(dfppe)(mu-Cl)(3)Ru(dmso-S)(3)](dfppe = 1,2-bis(dipentafluorophenyl phosphino)ethane (C6F5)(2)PCH2CH2P(C6F5)(2); dmso = dimethyl sulfoxide) (1) or RuCl(dfppe)(mu-Cl)(3)RuCl(dfppe)] (2) affords the mononuclear species trans-RuCl2(bpy)(dfppe)] (3). Using this precursor complex (3), a series of new cationic Ru(II) electrophilic complexes RuCl(L)(bpy)(dfppe)]Z] (L = P(OMe)(3) (5), PMe3 (6), CH3CN (7), CO (8), H2O (9); Z = OTf (5, 6, 7, 8), BAr4F (9) have been synthesized via abstraction of chloride by AgOTf or NaBAr4F in the presence of L. Complexes 5 and 6 were converted into the corresponding isomeric hydride derivatives RuH(PMe3)(bpy)(dfppe)]OTf] (10a, 10b) and RuH(P(OMe)(3))(bpy)(dfppe)]OTf] (11a, 11b) respectively, when treated with NaBH4. Protonation of the cationic monohydride complex (11a) with HOTf at low temperatures resulted in H-2 evolution accompanied by the formation of either solvent or triflate bound six coordinated species Ru(S)(P(OMe)(3))(bpy)(dfppe)]OTf](n) (S = solvent (n = 2), triflate (n = 1)] (13a/13b); these species have not been isolated and could not be established with certainty. They (13a/13b) were not isolated, instead the six-coordinated isomeric aqua complexes cis-(Ru(bpy)(dfppe)(OH2)(P(OMe)(3))]OTf](2) (14a/14b) were isolated. Reaction of the aqua complexes (14a/14b) with 1 atm of H-2 at room temperature in acetone-d(6) solvent resulted in heterolytic cleavage of the H-H bond. Results of the studies on H-2 lability and heterolytic activation using these complexes are discussed. The complexes 3, 5, 11a, and 14a have been structurally characterized.

Photoluminescence, thermoluminescence and EPR studies of solvothermally derived Ni2+ doped Y(OH)(3) and Y2O3 multi-particle-chain microrods

Rod like structures of hexagonal Y(OH)(3):Ni2+ and cubic Y2O3:Ni2+ phosphors have been successfully synthesized by solvothermal method. X-ray diffraction studies of as-formed product shows hexagonal phase, whereas the product heat treated at 700 degrees C shows pure cubic phase. Scanning electron micrographs (SEM) of Y(OH)(3):Ni2+ show hexagonal rods while Y2O3:Ni2+ rods were found to consist of many nanoparticles stacked together forming multi-particle-chains. EPR studies suggest that the site symmetry around Ni2+ ions is predominantly octahedral. PL spectra show emission in blue, green and red regions due to the T-3(1)(P-3)->(3)A(2)(F-3), T-1(2)(D-1)->(3)A(2)(F-3) and T-1(2)(D-1)-> T-3(2)(F-3) transitions of Ni2+ ions, respectively. TL studies were carried out for Y(OH)(3):Ni2+ and Y2O3:Ni2+ phosphor upon gamma-dose for 1-6 kGy. A single well resolved glow peaks at 195 and 230 degrees C were recorded for Y(OH)(3):Ni2+ and Y2O3:Ni2+, respectively. The glow peak intensity increases linearly up to 4 kGy and 5 kGy for Y(OH)(3):Ni2+ and Y2O3:Ni2+, respectively. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were estimated by different methods. The phosphor follows simple glow peak structure, linear response with gamma dose, low fading and simple trap distribution, suggesting that it is quite suitable for radiation dosimetry. (C) 2014 Elsevier B.V. All rights reserved.

Synthesis, DNA binding, docking and photocleavage studies of quinolinyl chalcones

A series of simple quinoline-chalcone conjugates have been synthesized by Claisen-Schmidt condensation reactions of substituted acetophenones with 2-chloro-3-formyl-quinoline and evaluated for their nucleolytic activity. The structures of the synthesized quinoline-chalcone conjugates were confirmed by IR, H-1 NMR, C-13 NMR and mass spectral analyses. Most of the prepared compounds showed significant DNA binding and photocleavage activities. The incorporation of an electron-donating group into ring A caused a moderate increase in the DNA binding and photocleavage activities. Compounds 3c and 3d exhibited promising DNA photocleavage against pUC 19 DNA with 85% inhibition at 100 mu M concentration. A structure-activity relationship analysis of these compounds was performed; compounds 3c and 3d are potential candidates for future drug discovery and development.

Low temperature magnetoresistance and magnetization studies of iron encapsulated multiwall carbon nanotube/polyvinyl chloride composites

We present the experimental results of temperature dependent magnetoresistance (MR) and the magnetization studies of iron encapsulated multiwall carbon nanotube (MWCNT)/polyvinyl chloride (PVC) composites with different wt% of MWCNTs. Transmission electron microscopy characterization shows that MWCNTs are encapsulated with rod-shaped iron nanoparticles of aspect ratio of similar to 3. The MR behavior of 1.9 wt% MWCNT/PVC sample shows dominance of forward scattering and wave function shrinkage whereas, weak localization and electron-electron interactions explain the MR data of higher wt% samples (9.1, 16.6 and 44.4 wt%). The composites of 4.7 and 9.1 wt% exhibit ferromagnetic behavior at all temperatures with room temperature coercivities of similar to 1036 and 628 Oe, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

Temperature-Dependent Magnetic and EPR Studies of Bulk and Nanoparticles of Bi0.1Ca0.9MnO3

We report temperature-dependent magnetic and electron paramagnetic resonance (EPR) properties of bulk and nanoparticle samples of Bi0.1Ca0.9MnO3 (BCMO). The nanoparticles of BCMO (dia similar to 50 nm) were prepared by the standard sol-gel technique and bulk samples by solid-state reaction method. We have investigated the magnetic ordering in the two samples by carrying out temperature-dependent magnetic and EPR studies and compared their properties. According to earlier reports, antiferromagnetic and ferromagnetic orders coexist in the bulk sample of Bi0.1Ca0.9MnO3. Our magnetization and EPR results show the existence of ferromagnetism in the bulk sample which is present in the nanosample as well but with somewhat weakened strength with the size reduction.

Preparation And Tribology Studies of Alkyl Carboxylic Acid Monolayer Films on Pei-Coated Glass Substrate

首次在涂敷PEI的玻璃表面上制备了癸酸及全氟癸酸的单分子层膜。研究了成膜机理及摩擦特性。结果表明。脱水剂DCCD促进了癸酸或全氟癸酸与PEI酞胺化的反应。导致两种羧酸在PEI表面产生了靠化学键（酞胺键）连接的稳定的单分子层膜,摩擦、磨损实验表明。单分子层有机膜的摩擦特性受膜的组成、表面能及有序性和堆积密度的重要影响。表面能越低,有序性和堆积密度越高。摩擦系数越低。与碳氢化合物相比。碳氟化合物形成的有序膜具有更高的强度和抗磨性能。

Friction and Wear Studies of Octadecyltrichlorosilane SAM on Silicon

A self-assembled monolayer of octadecyltrichlorosilane (OTS) was prepared on a single-crystal silicon wafer (111) and its tribological properties were examined with a one-way reciprocating tribometer. The worn surfaces and transfer film on the counterface were analyzed by means of scanning electron microscopy and X-ray photoelectron spectroscopy. The results show that, due to the wear of the OTS monolayer and the formation of the transfer film on the counterpart ball, the friction coefficient gradually increases from 0.06 to 0.13 with increasing sliding cycles and then keeps stable at a normal load of 0.5N. The transfer film is characterized by deposition, accumulation, and spalling at extended test duration. Though low friction coefficients of the monolayer in sliding against steel or ceramic counterfaces are recorded, poor load-carrying capacity and antiwear ability are also shown. Moreover, the monolayer itself or the corresponding transfer film on the counterface fails to lubricate even at a normal load of 1.0 N. Thus, the self-assembled monolayer of octadecyltrichlorosilane can be a potential boundary lubricant only at very low loads.

Preparation and Tribological Studies of Stearic Acid Self-Assembled Monolayers on Polymer-Coated Silicon Surface

We present a good alternative method to improve the tribological properties of polymer films by chemisorbing a long-chain monolayer on the functional polymer surface. Thus, a novel self-assembled monolayer is successfully prepared on a silicon substrate coated with amino-group-containing polyethyleneimine (PEI) by the chemical adsorption of stearic acid (STA) molecules. The formation and structure of the STA-PEI film are characterized by means of contact-angle measurement and ellipsometric thickness measurement, and of Fourier transformation infrared spectrometric and atomic force microscopic analyses. The micro- and macro-tribological properties of the STA-PEI film are investigated on an atomic force microscope (AFM) and a unidirectional tribometer, respectively. It has been found that the STA monolayer about 2.1-nm thick is produced on the PEI coating by the chemical reaction between the amino groups in the PEI and the carboxyl group in the STA molecules to form a covalent amide bond in the presence of N,N'-dicyclohexylcarbodiimide (DCCD) as a dehydrating regent. By introducing the STA monolayer, the hydrophilic PEI polymer surface becomes hydrophobic with a water contact angle to be about 105degrees. Study of the time dependence of the film formation shows that the adsorption of PEI is fast, whereas at least 24 h is needed to generate the saturated STA monolayer. Whereas the PEI coating has relatively high adhesion, friction, and poor anti-wear ability, the STA-PEI film possesses good adhesive resistance and high load-carrying capacity and anti-wear ability, which could be attributed to the chemical structure of the STA-PEI thin film. It is assumed that the hydrogen bonds between the molecules of the STA-PEI film act to stabilize the film and can be restored after breaking during sliding. Thus, the self-assembled STA-PEI thin film might find promising application in the lubrication of micro-electromechanical systems (MEMS).

Theoretical and experimental studies of the bell-jar-top inductively coupled plasma

The present paper describes a systematic study of argon plasmas in a bell-jar inductively coupled plasma (ICP) source over the range of pressure 5-20 mtorr and power input 0.2-0.5 kW, Experimental measurements as well as results of numerical simulations are presented. The models used in the study include the well-known global balance model (or the global model) as well as a detailed two-dimensional (2-D) fluid model of the system, The global model is able to provide reasonably accurate values for the global electron temperature and plasma density, The 2-D model provides spatial distributions of various plasma parameters that make it possible to compare with data measured in the experiments, The experimental measurements were obtained using a tuned Langmuir double-probe technique to reduce the RF interference and obtain the light versus current (I-V) characteristics of the probe. Time-averaged electron temperature and plasma density were measured for various combinations of pressure and applied RF power, The predictions of the 2-D model were found to be in good qualitative agreement with measured data, It was found that the electron temperature distribution T-e was more or less uniform in the chamber, It was also seen that the electron temperature depends primarily on pressure, but is almost independent of the power input, except in the very low-pressure regime. The plasma density goes up almost linearly with the power input.

Summary report on water quantity and quality studies of Vancouver Lake, Washington

Vancouver Lake, located adjacent to the Columbia River and just north of the Vancouver-Portland metropolitan area, is a "dying" lake. Although all lakes die naturally in geologic time through the process of eutrophication,* Vancouver Lake is dying more rapidly due to man's activities and due to the resultant increased accumulation of sediment, chemicals, and wastes. Natural eutrophication takes thousands of years, whereas man-made modifications can cause the death of a lake in decades. Vancouver Lake does, however, have the potential of becoming a valuable water resource asset for the area, due particularly to its location near the Columbia River which can be used as a source of "flushing" water to improve the quality of Vancouver Lake. (Document pdf contains 59 pages) Community interest in Vancouver Lake has waxed and waned. Prior to World War II, there were relatively few plans for discussions about the Lake and its surrounding land area. A plan to drain the Lake for farming was prohibited by the city council and county commissioners. Interest increased in 1945 when the federal government considered developing the Lake as a berthing harbor for deactivated ships at which time a preliminary proposal was prepared by the City. The only surface water connection between Vancouver Lake and the Columbia River, except during floods, is Lake River. The Lake now serves as a receiving body of water for Lake River tidal flow and surface flow from creeks and nearby land areas. Seasonally, these flows are heavily laden with sediment, septic tank drainage, fertilizers and drainage from cattle yards. Construction and gravel pit operations increase the sediment loads entering the Lake from Burnt Bridge Creek and Salmon Creek (via Lake River by tidal action). The tidal flats at the north end of Vancouver Lake are evidence of this accumulation. Since 1945, the buildup of sediment and nutrients created by man's activities has accelerated the growth of the large water plants and algae which contribute to the degeneration of the Lake. Flooding from the Columbia River, as in 1968, has added to the deposition in Vancouver Lake. The combined effect of these human and natural activities has changed Vancouver Lake into a relatively useless body of shallow water supporting some wildlife, rough fish, and shallow draft boats. It is still pleasant to view from the hills to the east. Because precipitation and streamflow are the lowest during the summer and early fall, water quantity and quality conditions are at their worst when the potential of the Lake for water-based recreation is the highest. Increased pollution of the Lake has caused a larger segment of the community to become concerned. Land use and planning studies were undertaken on the Columbia River lowlands and a wide variety of ideas were proposed for improving the quality of the water-land environment in order to enhance the usefulness of the area. In 1966, the College of Engineering Research Division at Washington State University (WSU0 in Pullman, Washington, was contacted by the Port of Vancouver to determine possible alternatives for restoring Vancouver Lake. Various proposals were prepared between 1966 and 1969. During the summer and fall of 1967, a study was made by WSU on the existing water quality in the Lake. In 1969, the current studies were funded to establish a data base for considering a broad range of alternative solutions for improving the quantity and quality of Vancouver Lake. Until these studies were undertaken, practically no data on a continuous nature were available on Vancouver Lake, Lake River, or their tributaries. (Document pdf contains 59 pages)

Ecologic and hydrographic studies of Elkhorn Slough, Moss Landing Harbor and near coastal waters, July 1974 to June 1976

In July 1974, we began a two-year baseline study of the Moss Landing Elkhorn Slough marine environment for Pacific Gas and Electric Company as mandated by the Coastal Commission. The original proposal included strong recommendations for more complete oceanographic studies and a third year of data collection. These further studies were not funded. This report is divided into three sections: oceanography, benthic invertebrate ecology and fish and zooplankton ecology. (PDF contains 480 pages)

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Mechanistic and kinetic studies of the surface chemistry of iridium and ruthenium

Quantitative investigations of the mechanisms and the kinetics of the surface-catalyzed activation of C-H, N-H, C-C, and C-N bonds on the close-packed surfaces of Ir(111) and Ru(001) have been performed. The interaction of CH_3NH_2 with Ru(001) was investigated in ultrahigh vacuum with the techniques of high-resolution electron energy loss spectroscopy and thermal desorption mass spectrometry. Activation of the central C-N bond is observed, but it is less favored than the competing channel of complete dehydrogenation, by a ratio between 2:1 to 3:1. The decomposition mechanism has been characterized with several surface intermediates and gas-phase products identified. A pronounced preference for the activation of C-H over N-H and C-N bonds has been established. Additionally, the kinetics of the initial dissociation of short chain alkanes on Ir(111) has been examined, and the rate parameters of the activation of C-C bonds and primary, secondary, and tertiary C-H bonds have been determined. The formation of primary alkyl products is favored, over most of the experimental temperature range, despite the thermodynamic preference for the activation of individual secondary and tertiary C-H bonds in comparison to individual primary C-H bonds. At higher surface temperatures, the activation of C-C bonds occurs at competitive rates to the C-H reaction channel. The measured deuterium kinetic isotope effect implicates substantial deformation of the terminal methyl group in the transition state of C-C bond cleavage. Finally, the surface structure sensitivity of C-H bond cleavage has been quantified for smooth (111) and corrugated (110) surfaces of iridium and platinum, as well as for step edge defect sites on Ir(111).

Robot navigation in dense crowds : statistical models and experimental studies of human robot cooperation

This thesis explores the problem of mobile robot navigation in dense human crowds. We begin by considering a fundamental impediment to classical motion planning algorithms called the freezing robot problem: once the environment surpasses a certain level of complexity, the planner decides that all forward paths are unsafe, and the robot freezes in place (or performs unnecessary maneuvers) to avoid collisions. Since a feasible path typically exists, this behavior is suboptimal. Existing approaches have focused on reducing predictive uncertainty by employing higher fidelity individual dynamics models or heuristically limiting the individual predictive covariance to prevent overcautious navigation. We demonstrate that both the individual prediction and the individual predictive uncertainty have little to do with this undesirable navigation behavior. Additionally, we provide evidence that dynamic agents are able to navigate in dense crowds by engaging in joint collision avoidance, cooperatively making room to create feasible trajectories. We accordingly develop interacting Gaussian processes, a prediction density that captures cooperative collision avoidance, and a "multiple goal" extension that models the goal driven nature of human decision making. Navigation naturally emerges as a statistic of this distribution.

Most importantly, we empirically validate our models in the Chandler dining hall at Caltech during peak hours, and in the process, carry out the first extensive quantitative study of robot navigation in dense human crowds (collecting data on 488 runs). The multiple goal interacting Gaussian processes algorithm performs comparably with human teleoperators in crowd densities nearing 1 person/m², while a state of the art noncooperative planner exhibits unsafe behavior more than 3 times as often as the multiple goal extension, and twice as often as the basic interacting Gaussian process approach. Furthermore, a reactive planner based on the widely used dynamic window approach proves insufficient for crowd densities above 0.55 people/m². We also show that our noncooperative planner or our reactive planner capture the salient characteristics of nearly any dynamic navigation algorithm. For inclusive validation purposes, we show that either our non-interacting planner or our reactive planner captures the salient characteristics of nearly any existing dynamic navigation algorithm. Based on these experimental results and theoretical observations, we conclude that a cooperation model is critical for safe and efficient robot navigation in dense human crowds.

Finally, we produce a large database of ground truth pedestrian crowd data. We make this ground truth database publicly available for further scientific study of crowd prediction models, learning from demonstration algorithms, and human robot interaction models in general.

Morphometric, meristics and comparative studies of Chrysichthys nigrodigititus (Lacepede) from Lagos Lekki and Badagry Lagoons, Lagos State, south west Nigeria

Morphometric measurements, meristic counts and comparative studies of Chrysicthys nigrodigitatus samples from Lagos, Lekki, and Badagry Lagoons was carried out to determine the amount of variation among the species from the different locations using seven meristic and two morphometric characters. Significant differences were observed only between the headlength (F==14.02; P<00.05), number of anal rays (F=19.9; P<0.05) and of gill raker counts (F=142.0, 160.94; P<0.05). The differences observed in the meristic characters could be attributed to environmental and climatic differences of the three isolated sites and therefore phenotypic rather than genetic. This study is valuable for the selection of quality strains of fish species for aquaculture production