Conformational studies of the phosphazenyl side chain in cyclophosphazenes. Part 3. Crystal and molecular structure of N3P3Cl4(NEt2)(NPPh3)

The crystal structure of N3P3Cl4(NEt2)(NPPh3) has been determined. The crystals are orthorhombic, space group Pbca, with a= 8.208(1), b= 21.890(1), c= 31.722(2)Å, Z= 8, and m.p. = 146.5 °C. The structure was solved by direct methods and refined to a final R value of 0.045 for 2 025 independent reflections. The analysis reveals significant variations in the ring P–N bond lengths. The two nitrogenous substituents, NPPh3 and NEt2, reside on the same phosphorus atom. The latter, NEt2, has an almost exact type II conformation (the plane NC2 almost perpendicular to the local NPN plane)(the first observed for a dialkylamino-group in cyclophosphazenes), the former, NPPh3, deviates from type II towards type III (in type III the plane Pring–N–Pexo makes an angle of ca. 45° with the local N–P–N ring plane). The present structure is compared with others of triphenylphosphazenyl-cyclophosphazenes and the conformation of the NPPh3 substituent and its electron supply in the ground and perturbed states are discussed.

Hexa-arm star shaped hydrazone derivatives from hexakis(4-formylphenoxy)-cyclotriphosphazene core

A series of novel hexasubstituted cyclophosphazene hydrazones [N(3)P(3)(-OC(6)H(4)-p-CH=N-NH-C(O)-C(6)H(4)-p-X)(6)] (X = H, Br, Cl, F, OH, OCH(3), CH(3), NO(2), NH(2)) were prepared by a sixfold condensation reaction of [N(3)P(3)(-OC(6)H(4)-p-CHO)(6)] with para-substituted benzoic hydrazides [NH(2)-NH-C(O)-C(6)H(4)-p-X] with excellent yields (91-98%). The structures of the compounds were confirmed by elemental analysis, FT-IR, (1)H, (13)C, (31)P, 2D-HSQC NMR and mass spectrometry (MALDI-TOF). All the synthesized cyclophosphazene hydrazones exhibit high thermal stability. The crystal structure of a homogeneously substituted hexakis(4-formylphenoxy)-cyclotriphosphazene was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group P2(1)/n with a = 16.558(3) angstrom, b = 10.250(2) angstrom, c = 23.429(5) angstrom, alpha = gamma = 90.00 degrees, beta = 90.461(4)degrees, V = 3976.5(14) angstrom(3) and Z = 4. The R value is 0.0823 for 4290 observed reflections. The conformations of the 4-formylphenoxy-groups are different at the three phosphorus atoms. (C) 2011 Elsevier B.V. All rights reserved.

Studies of phosphazenes .11. syntheses and structures of bis(primary amino)hexachlorocyclotetraphosphazenes and their dimethylamino derivatives

The bis(amino)hexachlorocyclotetraphosphazenes, 2-trans-6-N4P4 (NHR)2Cl6, R [dbnd] Me, Pr n Pr i , Bu n , CH2Ph, Ph, are obtained from the reaction of N4P4Cl8 with four mol. equivalents of the appropriate amine. Isomers with 2,4-structures have been isolated for R [dbnd] Bu n , CH2Ph. The 1H and 31P NMR spectra of these bis(amino) compounds and of their dimethylamino derivatives, 2-trans-6-N4P4 (NMe2)6 (NHR)2 are discussed.

P3F92-: An All-Pseudo-pi* 2 pi-Aromatic

A qualitative MO analysis suggests (PH3)(3)(2-) as a candidate for an all-pseudo-pi* 2 pi-aromatic; however computational studies rule out its existence. Fluorine substitution which increases the contribution of p orbitals on P in the pseudo-pi* MO makes (PF3)(3)(2-) a minimum and an aromatic. The 2 pi aromaticity arising from the bonding combination of the three pseudo-pi* fragment MOs is comparable to that in C3O32- and is another example for the analogy between CO and PF3. The dianion (PF3)(3)(2-) forms the first example of a three-membered ring with all the vertices constituted by pentacoordinate phosphorus. The ability of PF3 to form the all-pseudo-pi* 2 pi-aromatic system is not shared by the heavier analogues, AsF3 and SbF3.

Cross-Hetero-Dehydrogenative Coupling Reaction of Phosphites: A Catalytic Metal-Free Phosphorylation of Amines and Alcohols

Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance.

Spontaneous Breaking of Time-Reversal Symmetry in Strongly Interacting Two-Dimensional Electron Layers in Silicon and Germanium

We report experimental evidence of a remarkable spontaneous time-reversal symmetry breaking in two-dimensional electron systems formed by atomically confined doping of phosphorus (P) atoms inside bulk crystalline silicon (Si) and germanium (Ge). Weak localization corrections to the conductivity and the universal conductance fluctuations were both found to decrease rapidly with decreasing doping in the Si: P and Ge: P delta layers, suggesting an effect driven by Coulomb interactions. In-plane magnetotransport measurements indicate the presence of intrinsic local spin fluctuations at low doping, providing a microscopic mechanism for spontaneous lifting of the time-reversal symmetry. Our experiments suggest the emergence of a new many-body quantum state when two-dimensional electrons are confined to narrow half-filled impurity bands.

Optical-Phonon-Limited High-Field Transport in Layered Materials

An optical-phonon-limited velocity model has been employed to investigate high-field transport in a selection of layered 2-D materials for both, low-power logic switches with scaled supply voltages, and high-power, high-frequency transistors. Drain currents, effective electron velocities, and intrinsic cutoff frequencies as a function of carrier density have been predicted, thus providing a benchmark for the optical-phonon-limited high-field performance limits of these materials. The optical-phonon-limited carrier velocities for a selection of multi-layers of transition metal dichalcogenides and black phosphorus are found to be modest compared to their n-channel silicon counterparts, questioning the utility of biasing these devices in the source-injection dominated regime. h-BN, at the other end of the spectrum, is shown to be a very promising material for high-frequency, high-power devices, subject to the experimental realization of high carrier densities, primarily due to its large optical-phonon energy. Experimentally extracted saturation velocities from few-layer MoS2 devices show reasonable qualitative and quantitative agreement with the predicted values. The temperature dependence of the measured v(sat) is discussed and compared with the theoretically predicted dependence over a range of temperatures.

PICES-GLOBEC International Program on Climate Change and Carrying Capacity: Report of 2001 BASS/MODEL, MONITOR and REX Workshops, and the 2002 MODEL/REX Workshop

Table of Contents [pdf, 0.22 Mb] Executive Summary [pdf, 0.31 Mb] Report of the 2001 BASS/MODEL Workshop [pdf, 0.65 Mb] To review ecosystem models for the subarctic gyres Report of the 2001 MONITOR Workshop [pdf, 0.7 Mb] To review ecosystem models for the subarctic gyres Workshop presentations: Sonia D. Batten PICES Continuous Plankton Recorder pilot project Phillip R. Mundy GEM (Exxon Valdez Oil Spill Trustee Council`s "Gulf Ecosystem Monitoring" initiative) and U.S. GOOS plans in the North Pacific Ron McLaren and Brian O`Donnell A proposal for a North Pacific Action group of the international Data Buoy Cooperation Panel Gilberto Gaxiola-Castrol and Sila Najera-Martinez The Mexican oceanographic North Pacific program: IMECOCAL Sydney Levitus Building global ocean profile and plankton databases for scientific research Report of the 2001 REX Workshop [pdf, 1.73 Mb] On temporal variations in size-at-age for fish species in coastal areas around the Pacific Rim Workshop presentations: Brian J. Pyper, Randall M. Peterman, Michael F. Lapointe and Carl J. Walters [pdf, 0.33 Mb] Spatial patterns of covariation in size-at-age of British Columbia and Alaska sockeye salmon stocks and effects of abundance and ocean temperature R. Bruce MacFarlane, Steven Ralston, Chantell Royer and Elizabeth C. Norton [pdf, 0.4 Mb] Influences of the 1997-1998 El Niño and 1999 La Niña on juvenile Chinook salmon in the Gulf of the Farallones Olga S. Temnykh and Sergey L. Marchenko [pdf, 0.5 Mb] Variability of the pink salmon sizes in relation with abundance of Okhotsk Sea stocks Ludmila A. Chernoivanova, Alexander N. Vdoven and D.V. Antonenko [pdf, 0.3 Mb] The characteristic growth rate of herring in Peter the Great Bay (Japan/East Sea) Nikolay I. Naumenko [pdf, 0.5 Mb] Temporal variations in size-at-age of the western Bering Sea herring Evelyn D. Brown [pdf, 0.45 Mb] Effects of climate on Pacific herring, Clupea pallasii, in the northern Gulf of Alaska and Prince William Sound, Alaska Jake Schweigert, Fritz Funk, Ken Oda and Tom Moore [pdf, 0.6 Mb] Herring size-at-age variation in the North Pacific Ron W. Tanasichuk [pdf, 0.3 Mb] Implications of variation in euphausiid productivity for the growth, production and resilience of Pacific herring (Clupea pallasi) from the southwest coast of Vancouver Island Chikako Watanabe, Ahihiko Yatsu and Yoshiro Watanabe [pdf, 0.3 Mb] Changes in growth with fluctuation of chub mackerel abundance in the Pacific waters off central Japan from 1970 to 1997 Yoshiro Watanabe, Yoshiaki Hiyama, Chikako Watanabe and Shiro Takayana [pdf, 0.35 Mb] Inter-decadal fluctuations in length-at-age of Hokkaido-Sakhalin herring and Japanese sardine in the Sea of Japan Pavel A. Balykin and Alexander V. Buslov [pdf, 0.4 Mb] Long-term variability in length of walley pollock in the western Bering Sea and east Kamchtka Alexander A. Bonk [pdf, 0.4 Mb] Effect of population abundance increase on herring distribution in the western Bering Sea Sergey N. Tarasyuk [pdf, 0.4 Mb] Survival of yellowfin sole (Limanda aspera Pallas) in the northern part of the Tatar Strait (Sea of Japan) during the second half of the 20th century Report of the 2002 MODEL/REX Workshop [pdf, 1.2 Mb] To develop a marine ecosystem model of the North Pacific Ocean including pelagic fishes Summary and Overview [pdf, 0.4 Mb] Workshop presentations: Bernard A. Megrey, Kenny Rose, Francisco E. Werner, Robert A. Klumb and Douglas E. Hay [pdf, 0.47 Mb] A generalized fish bioenergetics/biomass model with an application to Pacific herring Robert A. Klumb [pdf, 0.34 Mb] Review of Clupeid biology with emphasis on energetics Douglas E. Hay [pdf, 0.47 Mb] Reflections of factors affecting size-at-age and strong year classes of herring in the North Pacific Shin-ichi Ito, Yutaka Kurita, Yoshioki Oozeki, Satoshi Suyama, Hiroya Sugisaki and Yongjin Tian [pdf, 0.34 Mb] Review for Pacific saury (Cololabis saira) study under the VENFISH project lexander V. Leonov and Gennady A. Kantakov [pdf, 0.34 Mb] Formalization of interactions between chemical and biological compartments in the mathematical model describing the transformation of nitrogen, phosphorus, silicon and carbon compounds Herring group report and model results [pdf, 0.34 Mb] Saury group report and model results [pdf, 0.46 Mb] Model experiments and hypotheses Recommendations [pdf, 0.4 Mb] Achievements and future steps Acknowledgements [pdf, 0.29 Mb] References [pdf, 0.32 Mb] Appendix 1. List of Participants [pdf, 0.32 Mb] Appendices 2-5. FORTRAN codes [pdf, 0.4 Mb] (Document pdf contains 182 pages)

Does Long-Term Macrophyte Management in Lakes Affect Biotic Richness and Diversity?

We hypothesize that the richness and diversity of the biota in Lake Moraine (42°50’47”N, 75°31’39”W) in New York have been negatively impacted by 60 years of macrophyte and algae management to control Eurasian watermilfoil ( Myriophyllum spicatum L.) and associated noxious plants. To test this hypothesis we compare water quality characteristics, richness and selected indicators of plant diversity, zooplankton, benthic macroinvertebrates and fish in Lake Moraine with those in nearby Hatch Lake (42°50’06”N, 75°40’67”W). The latter is of similar size and would be expected to have similar biota, but has not been subjected to management. Measurements of temperature, pH, oxygen, conductivity, Secchi transparency, calcium, total phosphorus and nitrites + nitrates are comparable. Taxa richness and the diversity indices applied to the aquatic macrophytes are similar in both lakes. (PDF has 8 pages.)

Nutrient Limitation of Periphyton in a Spring-Fed, Coastal Stream in Florida, USA.

There is strong evidence to suggest that ground-water nitrate concentrations have increased in recent years and further increases are expected along portions of the central Gulf coast of Florida. Much of the nitrate enriched groundwater is discharged into surface waters through numerous freshwater springs that are characteristic of the area and the potential for eutrophication of their receiving waters is a legitimate concern. To test the potential effects of elevated nutrient concentrations on the periphyton community an in situ nutrient addition experiment was conducted in the spring-fed Chassahowitzka River, FL, USA, during the summer of 1999. Plastic tubes housing arrays of glass microscope slides were suspended in the stream. Periphyton colonizing the microscope slides was subjected to artificial increases in nitrogen, phosphorus or a combination of both. Slides from each tube were collected at 3- to 4- day intervals and the periphyton communities were measured for chlorophyll concentration. The addition of approximately 10 μg/L of phosphate above ambient concentrations significantly increased the amount of periphyton on artificial substrates relative to controls; the addition of approximately 100 μg/L of nitrate above ambient concentrations did not. The findings from this experiment implicated phosphorus, rather than nitrogen, as the nutrient that potentially limits periphyton growth in this system.(PDF contains 4 pages.)

Niveles de nutrientes y pigmentos fotosintéticos en el Río de la Plata interior (55°-59°W 34°-36°S)

The "Río de la Plata" River is one of the less studied systems of the basin with respect to its biological and ecological aspects. Twenty four and twenty seven surface stations were sample on September 22-23 and November 22-23, 1982, respectively. The section studied is part of the zone called inner "Río de la Plata" River. The discharge was 29.000 m3/s in September and 45.200 m3/s in November. Total phosphorus (PT), total organic nitrogen (NOT), chemical oxygen demad (COT) and total cholrophyll were measured. Dissolved oxygen (DO), turbidity (TURB), pH and electrical conductivity (K20) were also measured at the surface with a HORIBA U7 sensor on November 1982. PT was 72-208 mg/m3 and 66-205 mg/m3 in September and November repectively; the higher values were near the Argentinian coast and the outer zone. NOT was 33-106 µM and 49-117 µM and CHL was 1.4-5.8 mg/m3 and 1.3-9.4 mg/m3. TURB was between 44 and 240 NTU in November; the maximun value were obseved in the central zone. Steep K20 gradients were found near both coast. The reduced organic carbon load into the lower and external part of the "Río de la Plata" River was estimated. (Document contains 40 pages.)

Water quality impacts of mechanical shredding of aquatic macrophytes

We examined the impacts of mechanical shredding (i.e.. shredding plants and leaving biomass in the system) of the water chestnut (Trapa natans) on water quality and nutrient mobilization in a control and experimental site in Lake Champlain (Vermont-New York). A 1-ha plot was mechanically shredded within 1 h on 26 July, 1999. Broken plant material was initially concentrated on the lake surface of the experimental station after shredding, and was noticeable on the lake surface for 19 d. Over a two week period after shredding. concentrations of total nitrogen (N) and phosphorus (P), and soluble reactive P increased in the lower water column of the experimental station, coinciding with decomposition of water chestnut. Sediments in the control and experimental stations exhibited vet-v low rates of N and P release and could not account for increases in nutrient concentrations in the water column after mechanical shredding. Shredded plant material deployed in mesh bags at the experimental station lost similar to 70% of their total mass, and 42%, N and 70% P within 14 d. indicating Substantial nutrient mobilization via autolysis and decomposition. Chlorophyll a concentrations increased to 35 g/L at the experimental station on day 7 after shredding, compared to a concentration of 4 g/L at the control station. suggesting uptake of mobilized nutrients by phytoplankton. Disruption Of the Surface canopy of water chestnut by shredding was associated with marked increases in turbidity and dissolved oxygen, suggesting increased mixing at the experimental site.

Some effects of tropical storm Agnes on water quality in the Patuxent River estuary

A post Agnes study emphasizing environmental factors...weekly sampling at eight stations from 28 June to August 30, 1972. Spatial and temporal changes in the distribution of many factors, e.g., salinity, dissolved oxygen (DO), seston, particulate carbon and nitrogen, inorganic and organic fractions of dissolved nitrogen and phosphorus, and chlorophyll a were studied and compared to earlier extensive records. Patterns shown by the present data were compared especially with a local heavy storm that occurred in the Patuxent drainage basin during July 1963. Some interesting correlations were observed in the data. (PDF has 39 pages.)

Some effects of Hurricane Agnes on water quality in the Patuxent River Estuary

A post-Agnes study that emphasized environmental factors was carried out on the Patuxent River estuary with weekly sampling at eight stations from 28 June t o 30 August 1972. Spatial and temporal changes in the distribution of many factors , e.g., salinity , dissolved oxygen, seston, particulate carbon and nitrogen, inorganic and organic fractions of dissolved nitrogen and phosphorus, and chlorophyll a were studied and compared t o extensive earlier records. Patterns shown by the present data were compared especially with a local heavy storm that occurred in the Patuxent drainage basin during July 1969. Estimates were made of the amounts of material contributed via upland drainage. A first approximation indicated that 14.8 x l0 (3) metric tons of seston were contributed t o the head of the estuary between 21 and 24 June. (PDF contains 46 pages)

Effects of perturbations on estuarine microcosms

Microcosms containing planktonic communities from Chesapeake Bay responded to enrichment with sewage by developing larger standing crops of phytoplankton and zooplankton. Data suggest that increased productivity would be reflected up the food chain but might increase existing problems with dissolved oxygen and might lead to qualitative changes in the composition of the zooplankton. Either phosphorus or nitrogen was removed more rapidly from solution depending on where and when the experimental water was obtained. Increases in standing crop of algae were associated with loss of nitrogen from solution in two experiments and losses of both nitrogen and phosphorus from solution in one experiment.