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Volumn 13, Issue 34, 2007, Pages 9617-9636

On the characterization of dynamic supramolecular systems: A general mathematical association model for linear supramolecular copolymers and application on a complex two-component hydrogen-bonding system

Author keywords

Analytical methods; Mathematical chemistry; NMR spectroscopy; Polymers; Supramolecular chemistry

Indexed keywords

HYDROGEN BONDS; LINEAR ALGEBRA; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERS; REACTION KINETICS; SUPRAMOLECULAR CHEMISTRY;

EID: 36649022632     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200700032     Document Type: Article
Times cited : (21)

References (75)
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    • For dynamic systems, using method 1). the dissociation at internal positions will still take place when the ends are blocked. Using method 3. the disadvantage would be that the spectrum of possible monomers, those having acceptor and donor properties, respectively, is limited, thus limiting the number of different possible supramolecular polymers available.
    • For dynamic systems, using method 1). the dissociation at internal positions will still take place when the ends are blocked. Using method 3). the disadvantage would be that the spectrum of possible monomers, those having acceptor and donor properties, respectively, is limited, thus limiting the number of different possible supramolecular polymers available.
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    • The two-dimensional DOSY technique, method 2, is in many cases a solution for static (generally strong) supramolecular systems, where the diffusion coefficient D, of each species i in the first dimension can be identified by the NMR resonance spectrum in the second, providing information about the size of the aggregates.[7d.c] However, for dynamic (generally weak) supramolecular systems, both the observed diffusion coefficient and the observed NMR resonances consist of an average of the ones for all the different species weighted by the mole-fraction of each i, making the DOSY technique inappropriate. In contrast, if successful, for dynamic association systems studied by the corresponding one-dimensional technique, PFG NMR, association constants can be obtained: For example, the association constant for a simple 1:1 system have been estimated assuming that the diffusion constant for the host and host-guest complex can be set equal,[7c] however, a situati
    • [7c] however, a situation far from the case with dynamic supramolecular polymers.
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    • See references [15] and [24], and references therein.
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    • ESIMS of the equilibrium mixture was attempted but failed due to the fact that at the operating conditions for ESIMS. the solution is so diluted that the equilibrium system is far from the total concentration at which the mole fraction of cyclic trimer 7 is at its maximum. This means that for the actual system on which the ESIMS is recorded, not only the total concentration of species is low, but so is the concentration of 7
    • ESIMS of the equilibrium mixture was attempted but failed due to the fact that at the operating conditions for ESIMS. the solution is so diluted that the equilibrium system is far from the total concentration at which the mole fraction of cyclic trimer 7 is at its maximum. This means that for the actual system on which the ESIMS is recorded, not only the total concentration of species is low, but so is the concentration of 7.
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    • Cyclic structures of higher association degree are also feasible according to molecular modeling. However, due to the entropie penalty cost for their formation, they are less likely compared to the cyclic trimer
    • Cyclic structures of higher association degree are also feasible according to molecular modeling. However, due to the entropie penalty cost for their formation, they are less likely compared to the cyclic trimer.
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    • For excellent discussions about criteria for NMR-titrations, see: Design. Synthesis, and Evaluation of an Efficacious Functional Group Dyad. Methods and Limitations in the use of NMR for Measuring Host-Guest Interactions: C. S. Wilcox in Frontiers in Supramolecular Organic Chemistry and Photochemistry (Eds.: H.-J. Schneider, H. Dürr), Wiley-VCH, Weinheim, 1991, pp. 121-143
    • For excellent discussions about criteria for NMR-titrations, see: "Design. Synthesis, and Evaluation of an Efficacious Functional Group Dyad. Methods and Limitations in the use of NMR for Measuring Host-Guest Interactions": C. S. Wilcox in Frontiers in Supramolecular Organic Chemistry and Photochemistry (Eds.: H.-J. Schneider, H. Dürr), Wiley-VCH, Weinheim, 1991, pp. 121-143
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    • Care must be exercised in adding more equilibria to existing ones without having strong indications that such equilibria exist as this will add more parameters to the fit since the estimate of the variance of the fit increases monotonically with the number of parameters of the fit. See: P. J. Brockwell, R. A. Davis, Time series: Theory and Methods. 2nd ed, Springer. New York, 1991, p. 287
    • Care must be exercised in adding more equilibria to existing ones without having strong indications that such equilibria exist as this will add more parameters to the fit since the estimate of the variance of the fit increases monotonically with the number of parameters of the fit. See: P. J. Brockwell, R. A. Davis, Time series: Theory and Methods. 2nd ed., Springer. New York, 1991, p. 287.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.