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  • Physical Chemistry  (7)
  • COMMUNICATIONS AND RADAR  (2)
  • 1990-1994  (9)
  • 1965-1969
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 651-659 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility behaviour of β-cyclodextrin in aqueous mixtures was studied by determining the interactions between the co-solvent and water. Three clear classes of co-solvent are evident. In the first, including ethanol, tetrahydrofuran and acetone, there is formation of clathrate hydrates by the co-solvent. In these systems the solubilization is a maximum at the mole fraction corresponding to the minimum in the partial excess molar volume. The second class, including such solvents as dimethyl sulphoxide and pyridine, forms strong molecular complexes with water, and here a valley and a plateau region occur in the solubility values. In the third class, including formamide and urea, a steady increase in the solubility is observed. For these highly polar solvents no maxima are observed in intrinsic solvent properties such as the partial excess molar volume.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 905-914 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability of some Schiff-bases formed between PLP and different amino acids has been investigated in a wide range of pH. The kinetic constants of formation of these compounds and their hydrolysis rate constants have been determined. Results show that the α-position of the carboxyl group of amino acid plays an important role on the mechanism of water attack upon the C=N—bond. The absence of ionic groups in the surroundings of that bond must be an important factor of stability. Bulky hydrophobic substituents in the amino acid, near the amine part, protect the imine bond against hydrolysis.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 67-78 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the formation and hydrolysis of the Schiff base of pyridoxal-5′ -phosphate (PLP) and n-dodecylamine (DOD) by kinetic methods and found the formation rate constants to be much larger than those reported for related systems. This can be ascribed to the occurrence of local concentration of charges in the vicinity of the carbinolamine, which stabilizes the corresponding transition state of the dehydration reaction. On the other hand, the hydrolysis rate constants of our system were considerably smaller as a result of the 12-atom hydrocarbon chain acting as a bulky hydrophobic rest protecting the imine bond from attack by water.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1017-1026 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article presents the kinetic of formation of pentacyano(3-pyrazincarboxylate)ferrate(II) from pyrazincarboxylate and pentacyanoaquoferrate(II) ions in various isodielectric water-cosolvent mixtures at 298 K. The rate law is in the form d[Fe(CN)5(3-pzCO2)4-]/dt = kf[Fe(CN)5H2O-3] [pzCO2-]. Plots of log(kf/dm3 mol-1 s-1) vs. Dm-1 (where Dm is the bulk dielectric constant of the medium) and log(kf/dm3 mol-1 s-1) vs. the Grunwald-Winstein parameter are nonlinear for some of the mixtures and to each mixture corresponds a different behavior in respect to the above parameters. The plots of log(kf/dm3 mol-1 s-1) vs. the mol fraction of water are straight lines over the entire composition range studied, except for the water-methanol mixture. It is evident that the solvation phenomenon plays a dominant role and that the rate of formation is mediated by the dual solvent vectors, the overall basicity and acidity of the solvent mixtures.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 865-874 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study on the basic hydrolysis of cephaloridine at pD= 10.5 was carried out by using the 1H—NMR technique. Epimerization at H7, a nucleophilic attack of hydroxyl ion on the β-lactam carbonyl group followed by the release of the pyridine molecule, and isomerization of the double bond at position 3 in the dihydrothiazine ring were the major reactions observed.Based on the results obtained, it should be emphasized that the presence of a pyridine group at 3′ results in a slightly increased formation constant for the exo methylene compound relative to other cephalosporins with different substituents at that position.The activation energy for the epimerization constant and the cleavage of the β-lactam ring at pD 10.5 was 21.2 kcal/mol. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 6
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Salt effects on the oxidation of the iron(II) complexes Fe(CN)4(bpy)2-, cis-(CN)2(bpy)2 and Fe(bpy)32+ by S2O82- as well as on the reaction Fe2+ + Co(NH3)5Cl2+ have been studied in concentrated electrolyte solutions at 298.2 K. We have gone from anion-anion to cation-cation reaction with the intermediate cases of anion-neutral and cation-anion reactions. Results show that the main cause of the kinetic salt effects observed is the interaction between supporting electrolytes and the solvent. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 571-575 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of the title substrate with a series of secondary alicyclic amines are subjected to a kinetic study in 44 wt% aqueous ethanol, 25.0°C, and ionic strength 0.2 M (KCl). The Brönsted-type plot (log kN vs. pKa of the amine, where kN is the second-order rate coefficient) obtained is linear with slope β = 0.53, which indicates a concerted mechanism. The predicted Brönsted break for a hypothetical stepwise mechanism is pKa0 = 8.7, which was not observed (pKa range of amines: 6-11). The same reaction in water is stepwise, which shows that the tetrahedral intermediate found in water is much destabilized by the change of solvent from water to aqueous ethanol. © 1994 John Wiley & Sons, Inc.
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  • 8
    Publication Date: 2019-01-25
    Description: In recent years, Spread-Spectrum Code Division Multiple Access (CDMA) has become a very popular access scheme for mobile communications due to a variety of reasons: excellent performance in multipath environments, high scope for frequency reuse, graceful degradation near saturation, etc. In this way, a CDMA system can support simultaneous digital communication among a large community of relatively uncoordinated users sharing a given frequency band. Nevertheless, there are also important problems associated with the use of CDMA. First, in a conventional CDMA scheme, the signature sequences of asynchronous users are not orthogonal and, as the number of active users increases, the self-noise generated by the mutual interference between users considerably degrades the performance, particularly in the return link. Furthermore, when there is a large disparity in received powers - due to differences in slant range or atmospheric attenuation - the non-zero cross-correlation between the signals gives rise to the so-called near-far problem. This leads to an inefficient utilization of the satellite resources and, consequently, to a drastic reduction in capacity. Several techniques were proposed to overcome this problem, such as Synchronized CDMA - in which the signature sequences of the different users are quasi-orthogonal - and power control. At the expense of increased network complexity and user coordination, these techniques enable the system capacity to be restored by equitably sharing the satellite resources among the users. An alternative solution is presented based upon the use of time-reference adaptive digital beamforming on board the satellite. This technique enables a high number of independently steered beams to be generated from a single phased array antenna, which automatically track the desired user signal and null the unwanted interference source. In order to use a time-reference adaptive antenna in a communications system, the main challenge is to obtain a reference signal highly correlated with the desired user signal and uncorrelated with the interferences. CDMA lends itself very easily to the generation of such a reference signal, thanks to the a priori knowledge of the user's signature sequence. First, the integration of an adaptive antenna in an asynchronous CDMA system is analyzed. The adaptive antenna system can provide increased interference rejection - much higher than that afforded by the code alone - and, since CDMA is mainly interference limited, any reduction in interference converts directly and linearly into an increase in capacity. Analyses and computer simulations are presented that show how an asynchronous CDMA system incorporating adaptive beamforming can provide at least as much capacity as a synchronous system. More importantly, the proposed concept allows the near-far effect to be mitigated without requiring a tight coordination of the users in terms of transmitted power control or network synchronization. The system is extremely robust to the near-far effect because the signals reaching the satellite from directions other than that of the desired user - which are likely to have different power levels - are adaptively canceled by the antenna. Finally, a payload architecture is presented that illustrates the practical implementation of this concept. This digital payload architecture demonstrates that with the advent of high performance CMOS digital processing, the on-board implementation of complex DSP techniques - in particular Digital Beamforming - has become possible, being most attractive for Mobile Satellite Communications.
    Keywords: COMMUNICATIONS AND RADAR
    Type: JPL, Proceedings of the Third International Mobile Satellite Conference (IMSC 1993); p 43-44
    Format: text
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  • 9
    Publication Date: 2019-07-13
    Description: Code-Division Multiple-Access (CDMA) stands out as a strong contender for the choice of multiple access scheme in these future mobile communication systems. This is due to a variety of reasons such as the excellent performance in multipath environments, high scope for frequency reuse and graceful degradation near saturation. However, the capacity of CDMA is limited by the self-interference between the transmissions of the different users in the network. Moreover, the disparity between the received power levels gives rise to the near-far problem, this is, weak signals are severely degraded by the transmissions from other users. In this paper, the use of time-reference adaptive digital beamforming on board the satellite is proposed as a means to overcome the problems associated with CDMA. This technique enables a high number of independently steered beams to be generated from a single phased array antenna, which automatically track the desired user signal and null the unwanted interference sources. Since CDMA is interference limited, the interference protection provided by the antenna converts directly and linearly into an increase in capacity. Furthermore, the proposed concept allows the near-far effect to be mitigated without requiring a tight coordination of the users in terms of power control. A payload architecture will be presented that illustrates the practical implementation of this concept. This digital payload architecture shows that with the advent of high performance CMOS digital processing, the on-board implementation of complex DSP techniques -in particular digital beamforming- has become possible, being most attractive for Mobile Satellite Communications.
    Keywords: COMMUNICATIONS AND RADAR
    Type: ERA Conference on DSP: The Enabling Technology for Communications; Mar 09, 1993 - Mar 10, 1993; Amsterdam; Netherlands|JPL, Addendum to the Proceedings of the Third International Mobile Satellite Conference (IMSC 1993); p 19-24
    Format: application/pdf
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