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  • Fluid Mechanics and Thermodynamics  (5)
  • General Chemistry
  • Life and Medical Sciences
  • 2000-2004  (8)
  • 1935-1939  (1)
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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 631-646 
    ISSN: 1434-1948
    Schlagwort(e): NLO materials ; Second harmonic generation ; Two-photon fluorescence ; Solvatochromism ; Electrochemistry ; Sesquifulvalene ; Sandwich complex ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In order to investigate nonlinear optical properties, in particular second harmonic generation (SHG) of organometallic complexes, numerous dipolar monocationic sesquifulvalene complexes of the general form [Mc-Z-C7H6]+ have been synthesised (Mc = metallocenyl), wherein the metallocenyl moiety Mc acts as an electron donor, and the tropylium cation C7H6+ as an electron acceptor. The mutual electronic influence of the donor and the acceptor groups is warranted by a linking spacer Z, which is a single bond [Mc = CpFeC5H4 (4a); Mc = CpRuC5H4 (4b)], an unsaturated bridge containing olefins [Z = (E-CH=CH)n: n = 1, Mc = CpFeC5H4 (25a), Mc = CpRuC5H4 (25b); n = 2, Mc = CpFeC5H4 (26); n = 3, Mc = CpFeC5H4 (27)], or thiophene units [Z = 2,5-C4H2S, Mc = CpFeC5H4 (28); Z = 5,5′-(2,2′-C4H2S)2, Mc = CpFeC5H4 (29); Z = 2-(5-E-CH=CH)C4H2S, Mc = CpFeC5H4 (30)]. For the salts of 4a·BF4, 4b·PF6 and 25a·PF6 X-ray structure determinations have been performed [4a·BF4: orthorhombic, Pnma, = 21.75(2), b = 9.900(2), c = 6.881(3) Å, V = 1482.0(15) Å3, Z = 4; 4b·PF6: monoclinic, P2(1)/c, a = 8.104(3), b = 18.206(14), c = 11.228(4) Å, β = 107.59(3), V = 1579.1(15) Å3, Z = 4; 25a·PF6: triclinic, P1bar, a = 10.067(6), b = 10.496(6), c = 11.418(6) Å, α = 94.07(4), β = 110.96(4), γ = 102.88(5)°, V = 1083.1(11) Å3, Z = 2]; the solid state structures indicate an almost coplanar arrangement of the organic π-system. Cyclic voltammetry studies reveal an irreversible one-electron reduction and an electrochemically reversible one-electron oxidation step for the ferrocenyl derivatives, whereas the ruthenocenyl derivatives demonstrate an irreversible two-electron oxidation. The redox potentials clearly indicate that the oxidation occurs at the metallocene unit, and the reduction is localised on the tropylium entity. In the electronic absorption spectra two intense bands are observed in the region 400 〈 λ 〈 900 nm which undergo strong negative solvatochromic shifts. The origin of the high-energy absorption band is assumed to be an interligand charge-transfer (LL-CT) transition, and the low-energy absorption band is assigned to a donor-acceptor charge-transfer (DA-CT) transition. Whereas the LL-CT is continuously shifted to lower energy with increasing spacer length, the energy of the DA-CT approaches a limiting value. A comparable phenomenon is also observed for the difference between the oxidation and reduction potentials obtained from electrochemical studies. Investigations concerning the nonlinear optical properties of the dipolar cationic sesquifulvalene complexes by means of hyper-Rayleigh scattering (HRS) indicate that the ferrocenyl derivatives fluoresce due to two-photon absorption whereas the ruthenocenyl congeners exhibit second harmonic generation with considerably larger first hyperpolarizability which is partly resonance-enhancement based.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 771-781 
    ISSN: 1434-1948
    Schlagwort(e): Cooperative effects ; Coordination modes ; Nickel ; Bimetallic complexes ; π interactions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Different cooperative binding modes of nitriles within the bimetallic pocket of a pyrazolate-based compartmental dinickel(II) site have been studied. The H3O2-bridged dinuclear complex 1 reacts with cyanamide to yield 4, in which a secondary hydrogencyanamido(1-) bridge spans the two metal centers at an unusually short metal-metal distance imposed by the primary ligand matrix. In 5, a single 2-cyanoguanidine (cnge) molecule is N-bound to one nickel(II) ion through its nitrile part and is coordinated to the adjacent metal site through an amido nitrogen. The characteristics of the coordination spheres of the metal centers suggest an additional side-on π-bonding interaction of the nitrile moiety with the second high-spin nickel(II) ion. This unusual interaction is corroborated by comparing the IR bands for the ν(C≡N) stretching vibration of 5 with those of complex 6, which has two end-on bound cnge molecules, and those of the related mononuclear complex 7, which lacks a second nickel(II) ion. The nature of the π-bonding interaction in 5 is further analyzed by DFT calculations on relevant model systems. Even though the π-bonding is found to be very weak, it does include some backbonding from occupied 3d MOs at the second high-spin nickel(II) ion to the π* MOs of the nitrile. Such an unconventional π-interaction is suggested to be enforced by the constrained fixation of the nitrile unit within the highly organized coordination pocket of the bimetallic framework. In contrast, the bifunctional 2-hydroxybenzonitrile is accommodated by the distinct binding of the nitrile and phenolate functions to the different metal centers in 8, which confirms that the simultaneous binding of both an OR-function and an end-on bound nitrile is indeed feasible within the active site pocket. Such a situation is reminiscent of the bimetallic effect that has been assumed to enable the cooperative hydration of nitriles at the dinickel(II) site of 1. Complexes 4·(ClO4)2, 5·(ClO4)2, 6·(ClO4)3, 7·(ClO4)(BPh4), and 8·(ClO4)2 have been characterized structurally by X-ray crystallography.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1434-1948
    Schlagwort(e): Lanthanide(III) ; Ytterbium ; Aryloxides ; Fluorine ; C-F Activation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction of [Yb(OAr)2(THF)3] (OAr = OC6H2-2,6-tBu2-4-R; R = H, Me, tBu) with perfluorodecalin in THF at room temperature results in C-F activation and formation of the first heteroleptic aryloxofluorolanthanoid complexes, [Yb(OAr)2F(THF)]2. Oxidation of bis(cyclopentadienyl)ytterbium(II) with perfluoro(methylcyclohexane) or perfluorodecalin in DME surprisingly gives unsolvated [YbCp2F]3. The analogous reaction of bis(methylcyclopentadienyl)ytterbium(II) yields unsolvated [Yb(MeCp)2F]4, whilst in THF, the oxidation provides [Yb(MeCp)2F(THF)]2. Treatment of [YbCp2F(THF)]2 with triphenylphosphane oxide gives [YbCp2F(OPPh3)]2. X-ray structure determinations revealed [Yb(OAr)2F(THF)]2 (R = H or tBu) to be centrosymmetric fluoride-bridged dimers with five-coordination for ytterbium. Examination of the structures of the cyclopentadienyl complexes showed that [YbCp2F]3 is trimeric with formal eight-coordination for ytterbium and a planar (YbF)3 ring, whereas [Yb(MeCp)2F]4 is an eight-coordinate tetramer having a puckered (YbF)4 ring with F-Yb-F angles of ca. 90° and Yb-F-Yb angles close to 180° [178.9(4), 168.4(3)°]. Both [Yb(MeCp)2F(THF)]2 and [YbCp2F(OPPh3)]2 are nine-coordinate fluoride-bridged dimers.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 52 (1939), S. 637-638 
    ISSN: 0044-8249
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 5
    Publikationsdatum: 2019-07-18
    Beschreibung: A localized precipitation network has been established over a 4000 sq km region of northern Alabama in support of local weather and climate research at the Global Hydrology and Climate Center (GHCC) in Huntsville. This Cooperative Huntsville-Area Rainfall Measurement (CHARM) network is comprised of over 80 volunteers who manually take daily rainfall measurements from 85 sites. The network also incorporates 20 automated gauges that report data at 1-5 minute intervals on a 24 h a day basis. The average spacing of the gauges in the network is about 6 kin, however coverage in some regions benefit from gauges every 1-2 km. The 24 h rainfall totals from the CHARM network have been used to validate Stage III rainfall estimates of daily and storm totals derived from the WSR-88D radars that cover northern Alabama. The Stage III rainfall product is produced by the Lower Mississippi River Forecast Center (LMRFC) in support of their daily forecast operations. The intercomparisons between the local rain gauge and the radar estimates have been useful to understand the accuracy and utility of the Stage III data. Recently, the Stage III and CHARM rainfall measurements have been combined to produce an hourly rainfall dataset at each CHARM observation site. The procedure matches each CHARM site with a time sequence of Stage III radar estimates of precipitation. Hourly stage III rainfall estimates were used to partition the rain gauge values to the time interval over which they occurred. The new hourly rain gauge dataset is validated at selected points where 1-5 minute rainfall measurements have been made. This procedure greatly enhances the utility of the CHARM data for local weather and hydrologic modeling studies. The conference paper will present highlights of the Stage III intercomparison and some examples of the combined radar / rain gauge product demonstrating its accuracy and utility in deriving an hourly rainfall product from the 24 h CHARM totals.
    Schlagwort(e): Fluid Mechanics and Thermodynamics
    Materialart: 16th Conference on Hydrology; Jan 13, 2002 - Jan 18, 2002; Orlando, FL; United States
    Format: text
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  • 6
    Publikationsdatum: 2019-07-13
    Beschreibung: A fluid or fluid mixture, subjected to a vertical temperature and/or concentration gradient in a gravitational field, exhibits greatly enhanced light scattering at small angles. This effect is caused by coupling between the vertical velocity fluctuations due to thermal energy and the vertically varying refractive index. Physically, small upward or downward moving regions will be displaced into fluid having a refractive index different from that of the moving region, thus giving rise to the enhanced scattering. The scattered intensity is predicted to vary with scattering wave vector q, as q(sup -4), for sufficiently large q, but the divergence is quenched by gravity at small q. In the absence of gravity, the long wavelength fluctuations responsible for the enhanced scattering are predicted to grow until limited by the sample dimensions. It is thus of interest to measure the mean-squared amplitude of such fluctuations in the microgravity environment for comparison with existing theory and ground based measurements. The relevant wave vectors are extremely small, making traditional low-angle light scattering difficult or impossible because of stray elastically scattered light generated by optical surfaces. An alternative technique is offered by the shadowgraph method, which is normally used to visualize fluid flows, but which can also serve as a quantitative tool to measure fluctuations. A somewhat novel shadowgraph apparatus and the necessary data analysis methods will be described. The apparatus uses a spatially coherent, but temporally incoherent, light source consisting of a super-luminescent diode coupled to a single-mode optical fiber in order to achieve extremely high spatial resolution, while avoiding effects caused by interference of light reflected from the various optical surfaces that are present when using laser sources. Results obtained for a critical mixture of aniline and cyclohexane subjected to a vertical temperature gradient will be presented. The sample was confined between two horizontal parallel sapphire plates with a vertical spacing of 1 mm. The temperatures of the sapphire plates were controlled by independent circulating water loops that used Peltier devices to add or remove heat from the room air as required. For a mixture with a temperature gradient, two effects are involved in generating the vertical refractive index gradient, namely thermal expansion and the Soret effect, which generates a concentration gradient in response to the applied temperature gradient. For the aniline/cyclohexane system, the denser component (aniline) migrates toward the colder surface. Consequently, when heating from above, both effects result in the sample density decreasing with altitude and are stabilizing in the sense that no convective motion occurs regardless of the magnitude of the applied temperature gradient. The Soret effect is strong near a binary liquid critical point, and thus the dominant effect is due to the induced concentration gradient. The results clearly show the divergence at low q and the predicted gravitational quenching. Results obtained for different applied temperature gradients at varying temperature differences from the critical temperature, clearly demonstrate the predicted divergence of the thermal diffusion ratio. Thus, the more closely the critical point is approached, the smaller becomes the temperature gradient required to generate the same signal. Two different methods have been used to generate pure concentration gradients. In the first, a sample cell was filled with a single fluid, ethylene glycol, and a denser miscible fluid, water, was added from below thus establishing a sharp interface to begin the experiment. As time went on the two fluids diffused into each other, and large amplitude fluctuations were clearly observed at low q. The effects of gravitational quenching were also evident. In the second method, the aniline/cyclohexane sample was used, and after applying a vertical temperature gradient for several hours, the top and bottom temperatures were set equal and the thermal gradient died on a time scale of seconds, leaving the Soret induced concentration gradient in place. Again, large-scale fluctuations were observed and died away slowly in amplitude as diffusion destroyed the initial concentration gradient.
    Schlagwort(e): Fluid Mechanics and Thermodynamics
    Materialart: Sixth Microgravity Fluid Physics and Transport Phenomena Conference; 1; 325-344; NASA/CP-2002-211212/VOL1
    Format: application/pdf
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  • 7
    Publikationsdatum: 2019-07-13
    Beschreibung: A series of heated tube experiments was performed to investigate fluid instabilities that occur during heating of supercritical fluids. In these tests, JP-7 flowed vertically through small diameter tubes at supercritical pressures. Test section heated length, diameter, mass flow rate, inlet temperature, and heat flux were varied in an effort to determine the range of conditions that trigger the instabilities. Heat flux was varied up to 4 BTU/sq in./s, and test section wall temperatures reached as high as 1950 F. A statistical model was generated to explain the trends and effects of the control variables. The model included no direct linear effect of heat flux on the occurrence of the instabilities. All terms involving inlet temperature were negative, and all terms involving mass flow rate were positive. Multiple tests at conditions that produced instabilities provided inconsistent results. These inconsistencies limit the use of the model as a predictive tool. Physical variables that had been previously postulated to control the onset of the instabilities, such as film temperature, velocity, buoyancy, and wall-to-bulk temperature ratio, were evaluated here. Film temperatures at or near critical occurred during both stable and unstable tests. All tests at the highest velocity were stable, but there was no functional relationship found between the instabilities and velocity, or a combination of velocity and temperature ratio. Finally, all of the unstable tests had significant buoyancy at the inlet of the test section, but many stable tests also had significant buoyancy forces.
    Schlagwort(e): Fluid Mechanics and Thermodynamics
    Materialart: NASA/TM-2000-210345 , E-12392 , NAS 1.15:210345 , AIAA Paper 2000-3128 , Joint Propulsion; Jul 16, 2000 - Jul 19, 2000; Huntsville, AL; United States
    Format: application/pdf
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  • 8
    Publikationsdatum: 2019-07-11
    Beschreibung: The time profile (Delta)T(t) of the temperature difference, measured across a very compressible fluid layer of supercritical He-3 after the start of a heat flow, shows a damped oscillatory behavior before steady state convection is reached. The results for (Delta)T(t) obtained from numerical simulations and from laboratory experiments are compared over a temperature range where the compressibility varies by a factor of approx. = 40. First the steady-state convective heat current j(sup conv) as a function of the Rayleigh number R(alpha) is presented, and the agreement is found to be good. Second, the shape of the time profile and two characteristic times in the transient part of (Delta)T(t) from simulations and experiments are compared, namely: 1) t(sub osc), the oscillatory period and 2) t(sub p), the time of the first peak after starting the heat flow. These times, scaled by the diffusive time tau(sub D) versus R(alpha), are presented. The agreement is good for t(sup osc)/tau(sub D), where the results collapse on a single curve showing a powerlaw behavior. The simulation hence confirms the universal scaling behavior found experimentally. However for t(sub p)/tau(sub D), where the experimental data also collapse on a single curve, the simulation results show systematic departures from such a behavior. A possible reason for some of the disagreements, both in the time profile and in t(sub p) is discussed. In the Appendix a third characteristic time, t(sub m), between the first peak and the first oscillation minimum is plotted and a comparison between the results of experiments and simulations is made.
    Schlagwort(e): Fluid Mechanics and Thermodynamics
    Materialart: Proceedings of the 2003 NASA/JPL Workshop on Fundamental Physics in Space; 16-25; JPL-Pub-04-13
    Format: application/pdf
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  • 9
    Publikationsdatum: 2019-08-15
    Beschreibung: Late-time dynamics and morphology of a stratified turbulent shear layer are examined using 1) Reynolds-stress and heat-flux budgets, 2) the single-point structure tensors introduced by Kassinos et al. (2001), and 3) flow visualization via 3D volume rendering. Flux reversal is observed during restratification in the edges of the turbulent layer. We present a first attempt to quantify the turbulence-mean-flow interaction and to characterize the predominant flow structures. Future work will extend this analysis to earlier times and different values of the Reynolds and Richardson numbers.
    Schlagwort(e): Fluid Mechanics and Thermodynamics
    Materialart: Studying Turbulence Using Numerical Simulation Databases - IX: Proceedings of the 2002 Summer Program; 245-255
    Format: application/pdf
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