Guest-diffusion technique

Figure S.5 Picture of melt-blended films of LLDPE and 0.18% w/w Cl-RG (top) and Cl-YB (bottom) stretched at room temperature to a draw ratio of 500%. Pictures were taken under excitation with UV light of a wavelength of 365 nm. The melt-processing technique produces films of much higher optical brightness and contrast than guest-diffusion techniques. Reproduced with permission from Ref [34].

This technique was employed to study the binding dynamics of Pyronine Y (31) and B (32) with /)-CD/ s The theoretical background for this particular system has been discussed with the description of the technique above. Separate analysis of the individual correlation curves obtained was difficult since the diffusion time for the complex could not be determined directly because, even at the highest concentration of CD employed, about 20% of the guest molecules were still free in solution. The curves were therefore analyzed using global analysis to obtain the dissociation rate constant for the 1 1 complex (Table 12). The association rate constant was then calculated from the definition of the equilibrium constant. 

The [PHTP]5[NPP] inclusion compound is particularly rich in the information available on guest and host low-dimensional ordering from diffuse scattering and the advent of modern synchrotron radiation techniques has allowed a detailed analysis of these phenomena in this system.20... 

Analyzing the self-diffusion behavior of guest molecules in a microporous catalyst by the combined application of pulsed-field gradient NMR selfdiffusion techniques reveals the spatial distribution of transport resistances over the catalyst particles. In the case of coke deposits on ZSM-5, the distribution of carbonaceous residues over the crystal was found to be a function of the crystal morphology, the time onstream, and the chemical nature of the coke-producing reactant. In the case of ZSM-5 modified by H3PO4, the spatial distribution of the P compounds over the ZSM-5 crystals can be determined by self-diffusion measurements. Location of transport hindrances in a zeolite framework is based on self-diffusion measurements, in... 

In summary, the combination of the two techniques provides the first direct proof that the molecular diffusion pathway through the pore system correlates with the pore orientation of the hexagonal structure. In addition, the influence of specific structural features of the host on the diffusion behavior of the guest molecules can be clearly seen. 

The various examples of photoresponsive supramolecular systems that have been described in this chapter illustrate how these systems can be characterized by steady-state and time-resolved spectroscopic techniques based on either absorption or emission of light. Pertinent use of steady-state methods can provide important information in a simple vay stoichiometry and stability constant(s) of host-guest complexes, evidence for the existence of photoinduced processes such as electron transfer, energy transfer, excimer formation, etc. Investigation of the dynamics of these processes and characterization of reaction intermediates requires in most cases time-resolved techniques. Time-resolved fluorometry and transient absorption spectroscopy are frequently complementary, as illustrated by the study of photoinduced electron transfer processes. Time-resolved fluorometry is restricted to phenomena whose duration is of the same order of magnitude as the lifetime of the excited state of the fluorophores, whereas transient absorption spectroscopy allows one to monitor longer processes such as diffusion-controlled binding. 

As schematically shown by Fig. 46a, ferrierite contains two mutually intersecting arrays of channels. In comparison with the strictly one-dimensional MOF crystals considered in the previous section, their analysis is additionally complicated by the existence of two rooflike parts on either side of the platelike main crystal body. It turned out, however, that these features did in no way complicate the method of analysis. Contrary to the MOFs, which required an additional activation step after each uptake experiment, methanol in ferrierite proved to be an ideal host-guest system, where one and the same crystal could alternately be subjected to adsorption and desorption without any perceptible change in the sorbate profiles. It were these special conditions under which interference microscopy could be developed to a technique of diffusion measurement in nanoporous materials of unprecedented power [63,65,70,71,88,89]. 

The association constants for CyD complexes with chiral guests are generally different and mostly quantitatively determined by the chemical shift titration experiments. However, as mentioned above, other NMR parameters, such as relaxation rates [10, 70] or self-diffusion coefficients, may also be used. Both those parameters were successfully applied for the enantiodifferentiation and determination of association constants in complexes of the trifluoroacetate salts of the enantiomers of amphetamine, ephedrine, and propranolol with 2,6-di-O-dodecyl-a-CyD and its p analogue [71]. The DOSY technique was employed for the determination of diffusion coefficients of enantiomers of cyclohexanone derivatives complexed with a-, j8-and y-CyDs as well as with their per-O-methylated analogues [72]. 

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