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Macrocyclic hosts

The analytical capability of these matrices has been demonstrated for chiral amines [12, 13]. The procedure is illustrated in Fig. 8-4 for the separation of NapEtNH " CIO . Concentrated methanol/dichloromethane solutions of the racemic mixture were placed on a column containing the chiral macrocycle host. The enantiomers of the ammonium salts were resolved chromatographically with mixtures of methanol and dichloromethane as the mobile phase. The amounts of R and S salts in each fraction were determined by polarimetry. Because the chiral supported macrocycle interacts more strongly with S salts, the R salt passes through the column first and the S salt last, as seen in Fig. 8-4. [Pg.211]

The formation and properties of a range of host-guest complexes involving macrocyclic hosts and non-metallic guests are described in the next chapter. [Pg.135]

Host-guest chemistry macrocyclic hosts and non-metallic guests... [Pg.136]

Pseudorotaxanes are precursors of both rotaxanes and catenanes they consist of a guest molecule threaded through a macrocyclic host. Stoppering both ends of the threaded molecule gives a rotaxane, cycliza-tion of the thread gives a catenane. Pseudorotaxane formation may occur by spontaneous self-assembly, or may be template-controlled. Anion size can be of paramount importance for such templates - Cl- is effective, Br, I- less good, and PFe ineffective when the recognition motif demands a small template (454). [Pg.136]

Clipping. The clipping method relies on the synthesis of the rotaxane by formation of the macrocycle (host) in the presence of a dumbbell shaped molecule. The partial macrocycle undergoes a ring closing reaction around the dumbbell shaped molecule, thereby forming the rotaxane. [Pg.161]

Active template methodology. In this method, recently explored by Leigh et al. [16, 17], the rotaxane is formed via synthesis of the guest molecule in the presence of the macrocyclic host, where the guest ions or organic molecules play an active template role in promoting rotaxane formation. [Pg.161]

Encapsulation of squaraine 23a in diastereomeric triptycene-based tetralactam macrocycles 24a and 24b was described in [61], The synthesis of the macrocyclic hosts was done by the reaction of pyridine-2,6-dicarbonyl dichloride and 2,7-diaminotriptycene in dry THF with Et3N. Macrocycles 24a and 24b readily form... [Pg.176]

The process of combining cyanine and squaraine dyes by encapsulation, or covalent or noncovalent attachment with macrocyclic hosts, macromolecules, and micro- or nano-particles is a promising way to design novel probes and labels with substantially improved properties and for the development of advanced fluorescence-based assays. Nevertheless, the physicochemical properties of these dye-compositions are strongly dependent on the dye structure as well as the nature of the host macrocycle, macromolecule, or particle. Finally, development of new methods to synthesize these tracers can also be considered a challenging task. [Pg.185]

On the contrary, cucurbiturils preferentially coniine charged, but not neutral, species. Cucurbiturils also possess cylindrical cavities suitable for the inclusion of organic molecules. Cucurbiturils are a family of macrocyclic host molecules consisting of methylene-bridged glucouril units (see Scheme 2.44). [Pg.134]

The magnitude becomes smaller because the chromophore is farther apart from the rim of the cavity of the chiral macrocyclic host. - (Adapted from Park et ah, 2002)... [Pg.642]

The Diels-Alder reaction is an important and widely used reaction in organic synthesis (Sauer and Sustmann, 1980), and in the chemical industry (Griffiths and Previdoli, 1993). Rate enhancement of this reaction has been achieved by the use of solvents such as water, surfactants, very high pressure, lithium amides, alkylammonium nitrate salts, and macrocyclic hosts (Sherman et ak, 1998). Diels-Alder reactions can be ran in neutral ionic liquids (such as 1-butyl-3-methylimidazolium trifluoromethanesulfo-nate, l-butyl-3-methylimidazolium hexafluorophophate, l-butyl-3-methylimidazolium tetrafluoroborate, and l-butyl-3-methylimidazolium lactate). Rate enhancements and selectivities are similar to those of reactions performed in lithium perchlorate-diethyl ether mixtures. [Pg.173]

The C-isomer of the macrocyclic host molecule 4 (Fig. 28) is bound to a single molecule of methanol via a bifurcated hydrogen bond, 0-0 = 2.988, 3.072 A. The shift in the IR frequency is only 89 cm-1 indicating a weak interaction. The C-isomer has all four ra-hydrogen atoms of the cyclohexane ring junctures lying on the same side... [Pg.150]

As stated above, systematic names of macrocyclic host molecules were absurdly complicated for routine discussions [22]. Therefore Vogtle proposed the name coronand for crown ethers, and that of coronates for their complexes while cryptand complexes were called cryptates . The corresponding noncyclic analogues are podands such as 64 [23] and podates, respectively. The cumbersome name podando-coronands (and correspondingly podando-coronates ) was proposed for lariat ethers [24] having at least one sidearm like 65. Examples of hemispherands 66 [25], cavitands 25 [26] and those of some other hosts are discussed in Chapter 7 in some detail, whilst the exceptional stability of fragile guests 4 [2a] and 67 [27] in the hemicarcerand 5 cavity are discussed in Chapters 1 and Section 7.3. [Pg.52]

In addition to macrocyclic hosts discussed above, many other molecules capable of selective complexation have been synthesized. They belong to so-called macrocyclic chemistry [30] encompassing crown ethers discussed in this Chapter, cryptands 61-63 [21], spherands 70 [31], cyclic polyamines 71 [32], calixarenes 18 [5], and other cyclophane cages such as 72 [33] to name but a few. Hemicarcerand 5 [2b] discussed in Chapter 1 and Section 7.3 also belongs to this domain. Typical macrocyclic host molecules are presented in Chapter 7. [Pg.52]

Macrocyclic host molecules, medium-sized aggregates (microemulsions, micelles,vesicles, etc.) and mesoporous materials as catalysts... [Pg.155]

Numerous macrocyclic hosts have been shown to exert the catalytic activity on the included guest. This activity can be even undesirable. For instance, as mentioned before, cyclodextrins 173 use as aspirin carrier proved unsuccessful... [Pg.155]

Both of the tetraaza[3.3.3.3]paracyclophane (1) and tetraaza[n.l.n.l]paracyclo-phane (n = 6, 7, 8 cf. 2) rings have frequently been used as fundamental molecular skeletons for preparation of functionalized macrocyclic hosts [24-36]. Formation of three-dimensionally extended hydrophobic cavities was approached by introducing multiple hydrocarbon branches into the macrocyclic skeletons. Multiple hydrophobic chains thus placed in a macrocycle must be extended in the same direction and undergo mutual association to attain their optimal hydrophobic interactions in aqueous media due to thermodynamic reasons, while in nonaqueous media they presumably assume a free and separated configuration to minimize their mutual steric interactions. Consequently, such hydrophobic branches may provide a large hydrophobic cavity in aqueous media. [Pg.137]

A biomembrane is an excellent example of supramolecular assemblies, in which various functional molecules are structurally organized for molecular recognition. In order to develop artificial supramolecular systems capable of mimicking biomembrane functions, it seems important to investigate molecular recognition by macrocyclic hosts embedded in synthetic bilayer membranes. [Pg.143]

The microenvironmental polarity parameters for ANS and TNS bound to various hosts are listed in Table 3. These values are independent of temperature over a range of 10-40 °C. In the absence of any macrocyclic hosts, ANS is bound to the membrane in its surface domain while TNS to the hydrogen-belt domain [60, 61] interposed between the polar surface region and the hydrophobic domain composed of double-chain segments in the light of the Ej values the microenvironments for the former and the latter are close to that provided by water ( = 1.000) and equivalent to that in ethanol ( = 0.654), respectively. Such a difference in microenvironmental polarity presumably comes from the difference in molecular shape TNS is more slender than ANS. [Pg.148]

There are many other reactions devised for oxygen transfer such as various oxidants combined with transition metals with or without macrocyclic hosts and industrial specific epoxidations using oxygen, to name just a few. [Pg.1224]

Cavities of macrocyclic hosts. For example, the cavities of crown ethers, cyclodextrins, calixaranes and other synthesized and naturally occurring macrocycles are several angstroms in size and are capable of recognizing the guest molecules. These microreactors can dramatically influence the rate and product distribution of certain reactions. [Pg.318]

Work by Leonard Barbour at Stellenbosch University, South Africa, has resulted in a coordination compound-based macrocyclic host (7.67) with a continuous channel conceptually analogous to 7.66... [Pg.469]


See other pages where Macrocyclic hosts is mentioned: [Pg.204]    [Pg.120]    [Pg.336]    [Pg.216]    [Pg.392]    [Pg.136]    [Pg.146]    [Pg.154]    [Pg.77]    [Pg.160]    [Pg.99]    [Pg.151]    [Pg.273]    [Pg.74]    [Pg.135]    [Pg.196]    [Pg.278]    [Pg.83]    [Pg.147]    [Pg.181]    [Pg.56]    [Pg.57]    [Pg.231]    [Pg.258]    [Pg.282]    [Pg.387]   
See also in sourсe #XX -- [ Pg.126 ]




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