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The synthesis and structural characterization of novel, "molecular basket"-type bridged cavitands is reported. The resorcin[4]arene-based container molecules feature well-defined cavities that bind a wide variety of cycloalkanes and alicyclic heterocycles. Association constants (K(a)) of the 1:1 inclusion complexes were determined by both (1)H NMR and isothermal titration calorimetry (ITC). The obtained K(a) values in mesitylene ranged from 1.7×10(2) M(-1) for cycloheptane up to 1.7×10(7) M(-1) for morpholine. Host-guest complexation by the molecular baskets is generally driven by dispersion interactions, C-H···π interactions of the guests with the aromatic walls of the cavity, and optimal cavity filling. Correlations between NMR-based structural data and binding affinities support that the complexed heterocyclic guests undergo additional polar C-O···C=O, N-H···π, and S···π interactions. The first crystal structure of a cavitand-based molecular basket is reported, providing precise information on the geometry and volume of the inner cavity in the solid state. Molecular dynamic (MD) simulations provided information on the size and conformational preorganization of the cavity in the presence of encapsulated guests. The strongest binding of heterocyclic guests, engaging in polar interactions with the host, was observed at a cavity filling volume of 63 ± 9%.
The synthesis and structural characterization of novel, "molecular basket"-type bridged cavitands is reported. The resorcin[4]arene-based container molecules feature well-defined cavities that bind a wide variety of cycloalkanes and alicyclic heterocycles. Association constants (K(a)) of the 1:1 inclusion complexes were determined by both (1)H NMR and isothermal titration calorimetry (ITC). The obtained K(a) values in mesitylene ranged from 1.7×10(2) M(-1) for cycloheptane up to 1.7×10(7) M(-1) for morpholine. Host-guest complexation by the molecular baskets is generally driven by dispersion interactions, C-H···π interactions of the guests with the aromatic walls of the cavity, and optimal cavity filling. Correlations between NMR-based structural data and binding affinities support that the complexed heterocyclic guests undergo additional polar C-O···C=O, N-H···π, and S···π interactions. The first crystal structure of a cavitand-based molecular basket is reported, providing precise information on the geometry and volume of the inner cavity in the solid state. Molecular dynamic (MD) simulations provided information on the size and conformational preorganization of the cavity in the presence of encapsulated guests. The strongest binding of heterocyclic guests, engaging in polar interactions with the host, was observed at a cavity filling volume of 63 ± 9%.
The article contains sections titled: 1. Introduction 1.1. The Chemical Senses 1.2. Definition 1.3. History 1.4. Odor Descriptors, Odor Thresholds, Odor Value 1.4.1. Qualitative Measurements 1.4.2. Quantitative Measurements 1.4.2.1. Odor Threshold 1.4.2.2. Odor Value 1.5. Regulations and Labeling Requirements 1.5.1. Flavors 1.5.2. Fragrances 2. Single Fragrance and Flavor Compounds 2.1. Aliphatic Compounds 2.1.1. Hydrocarbons 2.1.2. Alcohols 2.1.3. Aldehydes and Acetals 2.1.4. Ketones 2.1.5. Acids and Esters 2.1.6. Miscellaneous Compounds 2.2. Acyclic Terpenes 2.2.1. Hydrocarbons 2.2.2. Alcohols 2.2.3. Aldehydes and Acetals 2.2.4. Ketones 2.2.5. Acids and Esters 2.2.5.1. Geranyl and Neryl Esters 2.2.5.2. Linalyl and Lavandulyl Esters 2.2.5.3. Citronellyl Esters 2.2.6. Miscellaneous Compounds 2.3. Cyclic Terpenes 2.3.1. Hydrocarbons 2.3.2. Alcohols and Ethers 2.3.3. Aldehydes and Ketones 2.3.4. Esters 2.3.5. Miscellaneous Compounds 2.4. Other Cycloaliphatic Compounds 2.4.1. Alcohols 2.4.2. Aldehydes 2.4.3. Ketones 2.4.4. Esters 2.5. Aromatic Compounds 2.5.1. Hydrocarbons 2.5.2. Alcohols and Ethers 2.5.3. Aldehydes and Acetals 2.5.4. Ketones 2.5.5. Esters of Araliphatic Alcohols and Aliphatic Acids 2.5.6. Aromatic Acids 2.5.7. Esters Derived from Aromatic and Araliphatic Acids 2.5.7.1. Benzoates 2.5.7.2. Phenyl acetates 2.5.7.3. Cinnamates 2.5.8. Miscellaneous Compounds 2.6. Phenols and Phenol Derivatives 2.6.1. Phenols, Phenyl Esters, and Phenyl Ethers 2.6.2. Phenol Alcohols and their Esters 2.6.3. Phenol Aldehydes 2.6.4. Phenol Ketones 2.6.5. Phenol Carboxylates 2.7. O‐ and O, S‐Heterocycles 2.7.1. Cyclic Ethers 2.7.2. Lactones 2.7.3. Glycidates 2.7.4. Miscellaneous Compounds 2.8. N‐ and N, S‐Heterocycles 3. Natural Raw Materials in the Flavor and Fragrance Industry 3.1. Introduction 3.2. Isolation of Natural Fragrance and Flavor Concentrates 3.2.1. Essential Oils 3.2.2. Extracts 3.3. Survey of Natural Raw Materials 4. Quality Control 5. Economic Aspects 6. Toxicology and Environmental Aspects
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