The synthesis and spectroscopic characterization of self-assembled cylindrical capsule 1a x 1a of nanometer dimensions is described. Encapsulation studies of large organic guest molecules were performed by using 1H NMR sprectroscopy in [D12]mesitylene solution. In addition to the computational (MacroModel 5.5, Amber* force field) analysis of the capsule's shape and geometry, an experimental approach towards estimation of the internal cavity dimensions is described. This involves using series of homologous molecular "rulers" (e.g. aromatic amides 5a-i). The available space inside the capsule 1a x 1a can be estimated as 5.7 x 14.7 A (error +/- 0.2 A) with this technique. Dibenzoyl peroxide is readily encapsulated in [D12]mesitylene and was shown to be stable to decomposition for at least three days at 70 degrees C inside the capsule. Moreover, 1a x 1a prevents the encapsulated peroxide from oxidizing Ph3P or diphenyl carbazide present in solution. The normal chemical reactivity of the peroxide is restored by release from the capsule by DMF, a solvent that competes for the hydrogen bonds that hold the capsule together. The protection and release of encapsulated species augurs well for the application of capsules in catalysis and delivery.
Autocatalysis and chemical amplification are properties of living systems that can lead to increased responsiveness and to self-replication. Here we describe a synthetic system in which a unique form of reagent compartmentalization gives rise to nonlinear kinetics that are subject to the precise size- and shape-selectivity of the host. The reactivity is reminiscent of autocatalytic behaviour, in which there is no direct contact between reagents and products, and our approach offers a general way to impose complex chemical behaviour onto synthetic systems.
Two synthetic pathways towards 4′‐C‐acylthymidines are presented. These modified mononucleosides are precursors of the 2′‐deoxyribonucleotide 4′‐C‐radical. They were converted into their corresponding 3′‐O‐[(2‐cyanoethyl) N,N‐diisopropylphosphoramidites] 3a–c and incorporated in oligonucleotides by solid‐phase synthesis. The structure of some modified nucleosides was revealed by X‐ray crystal‐structure analysis.
Autocatalysis and chemical amplification are characteristic properties of living systems, and they give rise to behaviors such as increased sensitivity, responsiveness, and self-replication. Here we report a synthetic system in which a unique form of compartmentalization leads to nonlinear, autocatalytic behavior. The compartment is a reversibly formed capsule in which a reagent is sequestered. Reaction products displace the reagent from the capsule into solution and the reaction rate is accelerated. The resulting selfregulation is sensitive to the highly selective molecular recognition properties of the capsule.
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