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  • 1
    ISSN: 1573-5079
    Keywords: photosynthesis ; thermal emission ; P700 ; quantum yield ; energy conversion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Thermal emission and photochemical energy storage were examined in photosystem I reaction center/core antenna complexes (about 40 Chl a/P700) using photoacoustic spectroscopy. Satisfactory signals could only be obtained from samples bound to hydroxyapatite and all samples had a low signal-to-noise ratio compared to either PS I or PS II in thylakoid membranes. The energy storage signal was saturated at low intensity (half saturation at 1.5 W m-2) and predicted a photochemical quantum yield of 〉90%. Exogenous donors and acceptors had no effect on the signal amplitudes indicating that energy storage is the result of charge separation between endogenous components. Fe(CN)6 -3 oxidation of P700 and dithionite-induced reduction of acceptors FA-FB inhibited energy storage. These data are compatible with the hypothesis that energy storage in PS I arises from charge separation between P700 and Fe-S centers FA-FB that is stable on the time scale of the photoacoustic modulation. High intensity background light (160 W m-2) caused an irreversible loss of energy storage and correlated with a decrease in oxidizable P700; both are probably the result of high light-induced photoinhibition. By analogy to the low fluorescence yield of PS I, the low signal-to-noise ratio in these preparations is attributed to the short lifetime of Chl singlet excited states in PS I-40 and its indirect effect on the yield of thermal emission.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Photosynthesis research 29 (1991), S. 23-35 
    ISSN: 1573-5079
    Keywords: absorption cross-section ; P700 ; antenna size ; photosystem I ; photosynthetic unit size ; cation effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A procedure is described which permits determination of the absolute absorption cross-section of a photosynthetic unit from the kinetics of reaction center photo-oxidation under weak, continuous actinic illumination. The method was first tested on a simple model compound of known absorption cross-section. We then applied the technique to absorption cross-section and functional antenna size measurements in photosystem I (PS I). A kinetic model is presented that can be used to fit P700 photo-oxidation measurements and extract the effective photochemical rate constant. The procedure is shown to properly correct for sample scattering and for the presence of heterogeneous absorbers (pigments not functionally coupled to P700). The relevance of these corrections to comparisons of antenna size using techniques that measure ‘relative’ absorption cross-sections is discussed. Measurements on pea thylakoids in the presence and absence of 5 mM MgCl2 show a 45% increase in PS I absorption cross-section in unstacked thylakoids. Analysis of detergent-isolated ‘native’ PS I preparations (200 chlorophyll a+b/P700) clearly indicate that the preparation contains a broad distribution of antenna sizes. Finally, we confirm that Chlamydomonas reinhardtii strain LM3-A4d contains a PS I core antenna complex which binds only ∼60 chlorophyll a/P700, about half the functional size of the wild type complex. Limitations associated with calculation of functional antenna size from cross-section measurements are also discussed.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 707-715 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Resonance Raman spectra have been obtained at several uv wavelengths (200-266 nm) for poly(rA)-poly(rU), poly(dA-dU), poly(dA)-poly(dT), and poly(dA-dT), representing nucleic acid duplexes containing A-U and A-T base pairs with different stacking interactions and different backbone conformations. Frequency shifts are seen in the exocyclic modes corresponding to coupled C4=O and C5=C6 stretching of U and T, although the NH2 scissors frequency of A is unshifted relative to that of the mononucleotide. These frequency patterns are interpreted as the superposition of H bonding and dipole-dipole coupling effects. Strong hypochromism is seen for most of the ring modes, resulting from the absorption hypochromism and from shifts in the electronic transitions due to stacking. The effects are larger for A bands in the homopolymers than in the heteropolymer duplexes, reflecting the larger influence of A/A than A/U(T) stacking. Poly(rA)-poly(rU) stands out among these polymers in showing 10 cm-1 downshifts in one U and several A modes. These shifts may be related to the A form structural parameters of this duplex, but the physical mechanism is not obvious.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 3337-3346 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies have been carried out with the tosylate of the monomethyl ether of polyethylene glycol (MeO-PEG-OTs) and with low molecular weight models to assess whether the neighboring oxygen at position 3 or 6 provides the driving force for hydrolytic cleavage of these activated derivatives. Our results reveal that MeO-PEG-OTs undergoes hydrolysis by competitive pathways. Water directly displaces the tosylate group to give the original PEG alcohol and the oxygen at position 6 nucleophilically displaces the tosylate group to give a cyclic oxonium ion as an intermediate. This intermediate can react by three pathways. First, it can lead to the production of the original PEG alcohol by attack of water on a ring carbon; second, dioxane and a lower molecular weight PEG alcohol is produced by water attack at the nonring carbon next to the charged oxygen; and third dioxane can be displaced by the oxygen atom at position 6 in the chain.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1635-1649 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When, in a poly-α-olefin, the probability that a given placement be isotactic depends upon the tacticity of only a finite number of immediate predecessors, the resulting diastereosequence distribution obeys the theory of Markoff chains. When this is not the case, one says that the resulting diastereosequence distribution is non-Markoffian. A special case of a Markoffian distribution is given by a simple Markof chain in which the tacticity of a given placement is assumed to be affected by only the tacticity of the immediately preceding placement. Another special case is, of course, the Bernoulli trial distribution in which the probability that a given placement be isotactic is independent of the tacticity of all other placements. A high resolution NMR spectrum can sometimes yield a quantitative determination of the concentrations of isotactic and syndiotactic placements and the concentrations of the three types of possible adjacent pairs of such placements (i.e., isotactic, syndiotactic, and heterotactic pairs). When this is the case, the spectrum can be used to determine whether or not a given diastereosequence distribution is Bernoullian. However, because the longest diastereosequences whose concentration can be measured by NMR spectroscopy involve only two placements, an NMR spectrum cannot check whether a given non-Bernoullian distribution be simple Markoffian or Markoffian in general. In fact, non-Markoffian distributions are compatible with existing NMR spectra on polymers prepared by anionic polymerizations. In this paper we work within the framework of Kac's theory of stationary statistical processes and point out some general results which are valid for both Markoffian and non-Markoffian processes. The results are applied to NMR spectroscopy and it is pointed out which calculations used to check the self-consistency of NMR data and to obtain the mean length of closed diastereosequences are valid for both Markoffian and non-Markoffian distributions.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 36 (1990), S. 1457-1470 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A molecular-based statistical simulation program was developed to study the covariance terms involved in the mass balance equations for complex chemical reactions during mixing. Several closure theories were compared to the simulations and available experimental data. The simple closure by Brodkey and Lewalle was found to be an extension of Toor's analysis applied to two reactions. This closure does not satisfy the molar fluctuation balance equation and was found only to represent the high Reynolds number data of Li and Toor. This result led to examining other possible closures which were based on Damkoehler numbers, reaction rate constant ratios, and limiting forms of the covariance term. These closures also were inadequate. The second reaction's covariance term varied from the product of the average values for each component to the Brodkey and Lewalle value for the range of Reynolds numbers considered.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 27 (1996), S. 9-13 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Increasing of wear resistance of Ti-6Al-4V alloy by nitrogen implantationNitrogen ion implantation is used to improve the wear resistance of Ti-6Al-4V alloy. Different implantation doses up to 1 · 1018N+/cm2 and E = 170 KeV were used. The unimplanted and the implanted specimens were tested in a wear model system with oscillation loading. The results show, that the wear performance was influenced by implantation dose and also by mean pressure. It was found, that surfaces, which are produced by a high implantation dose (1 · 1018N+/cm2), exhibited greater were resistance than untreated Ti-6Al-4V alloy. The best wear behaviour was achieved by a high implantation dose (1 · 1018N+/cm2) and a low mean pressure (p =0.22 MPa) at the wear test. The difference between the wear rate of the untreated and of the implantated specimen can obtain a factor about 10. The effective depth of the implantation action is greater than the penetration depth of the nitrogen ions.
    Notes: Durch Implantation von Stickstoff-Ionen wurde die Randschicht der Ti-Al6-V4-Legierung mit dem Ziel der Verbesserung des Verschleißverhaltens modifiziert. Es wurde dazu mit unterschiedlichen Stickstoffdosen bis 1 · 1018N+/cm2 bei E = 170 keV implantiert. Die Modellverschleißuntersuchungen bei oszillierender Beanspruchung wiesen nach, daß die Implantationsdosis in Abhängigkeit von der im Tribosystem wirkenden mittleren Pressung den Verschleiß deutlich beeinflußt. Wird mit einer hohen Dosis (1 ·1018N+/cm2) implantiert und werden die Beanspruchungsbedingungen so gewählt, daß nur eine relativ geringe Pressung von p ≤ 0.22 MPa auftritt, dann ist mit einer Erhöhung der Verschleißbeständigkeit mindestens um den Faktor 10 zu rechnen. Für größere Pressungen nimmt die Erhöhung des Verschleißwiderstandes ab. Die verschleißmindernde Wirktiefe der Implantation liegt weit über der Eindringtiefe der implantierten Stickstoffionen.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0935-6304
    Keywords: GC-AED ; Sulfur ; FCC gasoline ; Compound-independent calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The identification and quantification of sulfur-containing compounds in gasoline has become an area of interest because of impending legislation regulating total sulfur levels in these fuels. To study the effects of catalyst type and catalytic conditions on gasoline sulfur distribution, a method has been developed employing both the compound-independent and element-specific response of the atomic emission detector (AED). Calibration and quantification can be accomplished even where standards are not available, owing to the nature of the AED response.Compounds were separated on a thick film polydimethylsiloxane column. An external calibration curve was applied to the area responses of individual sulfur components in the sulfur chromatogram, and the concentrations of each were calculated. Summation of these sulfur concentrations over the gasoline range yields the total sulfur content of the gasoline.The method is applicable to the determination of these compounds in raw crude oils, finished gasolines, fluid cracking catalyst (FCC) unit gasolines, and fluid catalytic cracking “model” compound studies. A prefractionating column was employed to remove heavy (〉C13) materials; prefractionation is not, however, necessary for distilled or commercial gasoline samples. Detection limits, linearity, detector stability, and accuracy are discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 859-863 
    ISSN: 0947-3440
    Keywords: myo-Inositol, racemate resolution ; Glycosylation, trichloroacetimidate method ; Tin(II) trifluoromethanesulfonate catalyst ; Oligosaccharide ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2:3,4:5-Di-O-cyclohexylidene-D-/L-myo-inositol (2) could be readily converted into 6-O- and 1-O-unprotected L- and D-myo-inositol derivatives L- and D-4 and L- and D-6, respectively. Their reaction with trichloroacetimidate 7 as galactosyl donor in the presence of tin(II) trifluoromethanesulfonate as catalyst afforded the desired α(1-6)- and α(1-1)-connected galactopyranosides 8, 11 and 12. Compound 11 could be readily deprotected to afford target molecule (galactinol) 1 in high overall yield; from 12, the diastereoisomer 13 was obtained.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0947-6539
    Keywords: electronic structure ; frontier orbitals ; metalloporphyrins ; radical cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of magnesium and zinc tetraarylporphyrins and their porphyrinoxidized derivatives were studied by UV/Vis, ESR, and resonance Raman spectroscopy at various temperatures. The series included tetra(meta-dichlorophenyl)porphyrinatozinc (5), tetra(ortho-dichlorophenyl)porphyrinatozinc (6), tetra(ortho-difluorophenyl)porphyrinatozinc and -magnesium (9 and 10), and tetra(pentafluorophenyl)porphyrinatozinc and -magnesium (7 and 8). The radical cations (3a-10a) were isolated by chemical one-electron oxidation of their neutral precursors (3-10). Despite the structural similarity of all these radicals, their electronic ground state varied within the series. The position of the chloro groups was found to play a key role. While the radical cation of the meta-dichloro-substituted derivative 5a exhibited A2u spectroscopic features, the ortho-dichlorophenyl derivative (6a) showed A1u spectral features. Radicals of the fluoro-substituted porphyrins, especially that of 10, were found to have state-admixed (A1u/A2u) electronic structures, and the relative contributions of the two states was found to vary with temperature and to depend on the axial ligand. The results indicate that the fluoro-substituted porphyrins are primarily A2u at low temperature, even though their room temperature spectroscopic features resemble those of A1u cations. The elucidation of factors that affect the electronic structures of the radicals in the present series is helpful in providing a greater understanding of the spin-spin interactions in the intermediates of heme-dependant enzymatic reactions and their synthetic analogues.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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