Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Performance study of a cesium iodide photocathode-based UV photon detector in Ar/CH4 mixture

The detection efficiency of a gaseous photomultiplier depends on the photocathode quantum efficiency and the extraction efficiency of photoelectrons into the gas. In this paper we have studied the performance of an UV photon detector with P10 gas in which the extraction efficiency can reach values near to those in vacuum operated devices. Simulations have been done to compare the percentage of photoelectrons backscattered in P10 gas as well as in the widely used neon-based gas mixture. The performance study has been carried out using a single stage thick gas electron multiplier (THGEM). The electron pulses and electron spectrum are recorded under various operating conditions. Secondary effects prevailing in UV photon detectors like photon feedback are discussed and its effect on the electron spectrum under different operating conditions is analyzed. (C) 2014 Chinese Laser Press

The cellular structure of a two-dimensional H2/O2/Ar detonation wave

In this paper, the cellular structure of a two-dimensional detonation wave in a low pressure H2/O2/Ar mixture calculated with a detailed chemical reaction model, high order scheme and high resolution grids is investigated. The regular cellular structure is produced about 1 ms after introducing perturbations in the reaction zone of a steady one-dimensional detonation wave. It is found from the present resolution study that the discrepancies concerning the structure type arising from the coarser grid employed can be resolved using a sufficiently fine grid size of 0.05 mm and below and shows a double-Mach-like strong-type configuration. During the structure evolution process, the structure configuration does not change much in the periods before and after the triple point collision. Through the triple point collision, three regular collision processes are observed and are followed by a quick change to the double-Mach-like configuration. The simulated structure tracks show that there are three different tracks associated with different triple points or the kink on the transverse wave. Comparisons with previous work and experiments indicate the presence of a strong structure for an ordinary detonation.

The Structure and Evolution of a Two-Dimensional H2/O2/Ar Cellular Detonation

This paper reports on two-dimensional numerical simulation of cellular detonation wave in a / / mixture with low initial pressure using a detailed chemical reaction model and high order WENO scheme. Before the final equilibrium structure is produced, a fairly regular but still non-equilibrium mode is observed during the early stage of structure formation process. The numerically tracked detonation cells show that the cell size always adapts to the channel height such that the cell ratio is fairly independent of the grid sizes and initial and boundary conditions. During the structural evolution in a detonation cell, even as the simulated detonation wave characteristics suggest the presence of an ordinary detonation, the evolving instantaneous detonation state indicates a mainly underdriven state. As a considerable region of the gas mixture in a cell is observed to be ignited by the incident wave and transverse wave, it is further suggested that these two said waves play an essential role in the detonation propagation.

Comparative observation of Ar, Ar-H-2 and Ar-N-2 DC arc plasma jets and their arc root behaviour at reduced pressure

Results observed experimentally are presented, about the DC arc plasma jets and their arc-root behaviour generated at reduced gas pressure without or with an applied magnetic field. Pure argon, argon-hydrogen or argon- nitrogen mixture was used as the plasma-forming gas. A specially designed copper mirror was used for a better observation of the arc-root behaviour on the anode surface of the DC non-transferred arc plasma torch. It was found that in the cases without an applied magnetic field, the laminar plasma jets were stable and approximately axisymmetrical. The arc-root attachment on the anode surface was completely diffusive when argon was used as the plasma-forming gas, while the arc-root attachment often became constrictive when hydrogen or nitrogen was added into the argon. As an external magnetic field was applied, the arc root tended to rotate along the anode surface of the non-transferred arc plasma torch.

Ar原子光电流效应的研究

<正> 在十种染料波长范围内对应阴极放电中Ar原子光电流谱进行了观察,比较了Ar与Ne光电流效应的异同,提出了理论模型,并求得了放电电流与激光功率关系。

空阴极放电中Ar光电流谱的研究

在十种染料的波长范围内对空阴极放电中Ar的光电流谱、光电流信号与时间、放电电流及入射激光功率关系进行了实验观测,比较了Ne与Ar光电流效应的异同,在其共同点的基础上讨论了Ne与Ar光电流效应的机理,提出了理论模型并求得了放电电流与入射激光功率密度的关系。

Legislação brasileira sobre poluição do ar

Consultoria Legislativa - Área XI - Meio Ambiente, e Direito Ambiental, Organização Territorial, Desenvolvimento Urbano e Regional.

Behavior of ar plasma formed in a high-density plasma source - an ecr reactor

In order to develop the ultra-large scale integration(ULSI), low pressure and high density plasma apparatus are required for etching and deposit of thin films. To understand critical parameters such as the pressure, temperature, electrostatic potential and energy distribution of ions impacting on the wafer, it is necessary to understand how these parameters are influenced by the power input and neutral gas pressure. In the present work, a 2-D hybrid electron fluid-particle ion model has been developed to simulate one of the high density plasma sources-an Electron Cyclotron Resonance (ECR) plasma system with various pressures and power inputs in a non-uniform magnetic field. By means of numerical simulation, the energy distributions of argon ion impacting on the wafer are obtained and the plasma density, electron temperature and plasma electrostatic potential are plotted in 3-D. It is concluded that the plasma density depends mainly on both the power input and neutral gas pressure. However, the plasma potential and electron temperature can hardly be affected by the power input, they seem to be primarily dependent on the neutral gas pressure. The comparison shows that the simulation results are qualitatively in good agreement with the experiment measurements.

Cruise Report NOAA Ship McARTHUR II Cruise AR-04-04: Leg 2 (June 1-12, 2004): A pilot survey of deepwater coral/sponge assemblages and their susceptibility to fishing/harvest impacts at the Olympic Coast National Marine Sanctuary (OCNMS)

Summary: The offshore shelf and canyon habitats of the OCNMS (Fig. 1) are areas of high primary productivity and biodiversity that support extensive groundfish fisheries. Recent acoustic surveys conducted in these waters have indicated the presence of hard-bottom substrates believed to harbor unique deep-sea coral and sponge assemblages. Such fauna are often associated with shallow tropical waters, however an increasing number of studies around the world have recorded them in deeper, cold-water habitats in both northern and southern latitudes. These habitats are of tremendous value as sites of recruitment for commercially important fishes. Yet, ironically, studies have shown how the gear used in offshore demersal fishing, as well as other commercial operations on the seafloor, can cause severe physical disturbances to resident benthic fauna. Due to their exposed structure, slow growth and recruitment rates, and long life spans, deep-sea corals and sponges may be especially vulnerable to such disturbances, requiring very long periods to recover. Potential effects of fishing and other commercial operations in such critical habitats, and the need to define appropriate strategies for the protection of these resources, have been identified as a high-priority management issue for the sanctuary. To begin addressing this issue, an initial pilot survey was conducted June 1-12, 2004 at six sites in offshore waters of the OCNMS (Fig. 2, average depths of 147-265 m) to explore for the presence of deep-sea coral/sponge assemblages and to look for evidence of potential anthropogenic impacts in these critical habitats. The survey was conducted on the NOAA Ship McARTHUR-II using the Navy’s Phantom DHD2+2 remotely operated vehicle (ROV), which was equipped with a video camera, lasers, and a manipulator arm for the collection of voucher specimens. At each site, a 0.1-m2 grab sampler also was used to collect samples of sediments for the analysis of macroinfauna (> 1.0 mm), total organic carbon (TOC), grain size, and chemical contaminants. Vertical profiles of salinity, dissolved oxygen (DO), temperature, and pressure were recorded at each site with a small SeaCat conductivity-temperature-depth (CTD) profiler. Niskin bottles attached to the CTD also obtained near-bottom water samples in support of a companion study of microbial indicators of coral health and general ecological condition across these sites. All samples except the sediment-contaminant samples are being analyzed with present project funds. Original cruise plans included a total of 12 candidate stations to investigate (Fig. 3). However, inclement weather and equipment failures restricted the sampling to half of these sites. In spite of the limited sampling, the work completed was sufficient to address key project objectives and included several significant scientific observations. Foremost, the cruise was successful in demonstrating the presence of target deepwater coral species in these waters. Patches of the rare stony coral Lophelia pertusa, more characteristic of deepwater coral/sponge assemblages in the North Atlantic, were observed for the first time in OCNMS at a site in 271 meters of water. A large proportion of these corals consisted of dead and broken skeletal remains, and a broken gorgonian (soft coral) also was observed nearby. The source of these disturbances is not known. However, observations from several sites included evidence of bottom trawl marks in the sediment and derelict fishing gear (long lines). Preliminary results also support the view that these areas are important reservoirs of marine biodiversity and of value as habitat for demersal fishes. For example, onboard examination of 18 bottom-sediment grabs revealed benthic infaunal species representative of 14 different invertebrate phyla. Twenty-eight species of fishes from 11 families, including 11 (possibly 12) species of ommercially important rockfishes, also were identified from ROV video footage. These initial discoveries have sparked considerable interests in follow-up studies to learn more about the spatial extent of these assemblages and magnitude of potential impacts from commercial-fishing and other anthropogenic activities in the area. It is essential to expand our knowledge of these deep-sea communities and their vulnerability to potential environmental risks in order to determine the most appropriate management strategies. The survey was conducted under a partnership between NOAA’s National Centers for Coastal Ocean Science (NCCOS) and National Marine Sanctuary Program (NMSP) and included scientists from NCCOS, OCNMS, and several other west-coast State, academic, private, and tribal research institutions (see Section 4 for a complete listing of participating scientists). (PDF contains 20 pages)

Survey report of NOAA Ship McArthur II cruises AR-04-04, AR-05-05 and AR-06-03: Habitat classification of side scan sonar imagery in support of deep-sea coral/sponge explorations at the Olympic Coast National Marine Sanctuary

Habitat mapping and characterization has been defined as a high-priority management issue for the Olympic Coast National Marine Sanctuary (OCNMS), especially for poorly known deep-sea habitats that may be sensitive to anthropogenic disturbance. As a result, a team of scientists from OCNMS, National Centers for Coastal Ocean Science (NCCOS), and other partnering institutions initiated a series of surveys to assess the distribution of deep-sea coral/sponge assemblages within the sanctuary and to look for evidence of potential anthropogenic impacts in these critical habitats. Initial results indicated that remotely delineating areas of hard bottom substrate through acoustic sensing could be a useful tool to increase the efficiency and success of subsequent ROV-based surveys of the associated deep-sea fauna. Accordingly, side scan sonar surveys were conducted in May 2004, June 2005, and April 2006 aboard the NOAA Ship McArthur II to: (1) obtain additional imagery of the seafloor for broader habitat-mapping coverage of sanctuary waters, and (2) help delineate suitable deep-sea coral/sponge habitat, in areas of both high and low commercial-fishing activities, to serve as sites for surveying-in more detail using an ROV on subsequent cruises. Several regions of the sea floor throughout the OCNMS were surveyed and mosaicked at 1-meter pixel resolution. Imagery from the side scan sonar mapping efforts was integrated with other complementary data from a towed camera sled, ROVs, sedimentary samples, and bathymetry records to describe geological and biological (where possible) aspects of habitat. Using a hierarchical deep-water marine benthic classification scheme (Greene et al. 1999), we created a preliminary map of various habitat polygon features for use in a geographical information system (GIS). This report provides a description of the mapping and groundtruthing efforts as well as results of the image classification procedure for each of the areas surveyed. (PDF contains 60 pages.)