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Intermolecular interactions, chiral

Both the N- (a-methylbenzy 1) stearamide and phospholipid systems as detailed above proved to be difficult systems with which to work. The inability of N- a-methylbenzy 1)stearamide to form stable monolayers or even to spread from the crystal on anything but very acidic subphases presents a significant technical challenge despite the presence of a chiral headgroup that is unobstructed by other molecular features. On the other hand, the phospholipid surfactants that spread to form stable films both from solution and from their bulk crystals on pure water subphases at ambient temperatures displayed no discernible enantiomeric discrimination in any film property. The chiral functionality on these biomolecules is apparently shielded from intermolecular interactions with other chiral centers to the extent... [Pg.77]

These differences reflect the conformations of (+)- and meso-isomers as they sit at the air-water interface. What is much harder to elucidate is the effect of stereochemistry on intermolecular interactions. How does changing the stereochemistry at one chiral center affect interactions between diastereomers Ab initio molecular orbital calculations have been used to address the problem of separating stereochemically dependent inter- and intra-molecular interactions in diastereomeric compounds (Craig et al., 1971). For example, diastereomeric compounds such as 2,3-dicyanobutane exhibit significant energetic dependence on intramolecular configuration about their chiral centers. So far, however, little experimental attention has been focused on this problem. [Pg.121]

The effects of temperature and added achiral diluent to C-l5 6,6 -A amide diacids can also be due to differences in intermolecular interactions based on the molecule s configuration. The arguments given above are based on the assumption that the different configurations, the stereochemistry at the chiral... [Pg.132]

It has been shown frequently that without the presence of strong intermolecular interactions, discotic molecules are highly mobile in the liquid crystalline state.1 They undergo both lateral as well as rotational translations, resulting in the absence of positional order. Similarly, such discotics also freely rotate in the columnar aggregates they form in solution. This lack of positional order in the columns accounts for the absence of chiral or helical supramolecular order. We will demonstrate this characteristic using results obtained for triphenylenes. [Pg.398]

Noncovalent interactions play a key role in biodisciplines. A celebrated example is the secondary structure of proteins. The 20 natural amino acids are each characterized by different structures with more or less acidic or basic, hydrophilic or hydrophobic functionalities and thus capable of different intermolecular interactions. Due to the formation of hydrogen bonds between nearby C=0 and N-H groups, protein polypeptide backbones can be twisted into a-helixes, even in the gas phase in the absence of any solvent." A protein function is determined more directly by its three-dimensional structure and dynamics than by its sequence of amino acids. Three-dimensional structures are strongly influenced by weak non-covalent interactions between side functionalities, but the central importance of these weak interactions is by no means limited to structural effects. Life relies on biological specificity, which arises from the fact that individual biomolecules communicate through non-covalent interactions." " Molecular and chiral recognition rely on... [Pg.152]

The situation is different for solvolysis reactions in most other solvents, where the intermolecular interactions between ions at an ion pair are stronger than the compensating interactions with solvent that develop when the ion pair separates to free ions. This favors the observation of racemization during solvolysis. There are numerous reports from studies on solvolysis in solvents with relatively low dielectric constant such as acetic acid, of polarimetric rate constants (fe , s ) for racemization of chiral substrates that greatly exceed the titrimetric rate constant (fet, s ) for formation of acid from the solvolysis reaction. ... [Pg.333]

Although the chiral recognition factor in such systems is relatively weak, there is no question that it is measurable and provides a useful approach to elucidating intermolecular interactions between nonreacting molecules. [Pg.197]

Besides, information on intermolecular interactions has been derived in these studies from complexation-induced shifts (CIS). The chemical shift is an indicator for the shielding of a nucleus and thus for the electronic state of a specific proton. Since the electronic environment may change on complexation, CIS can be used to monitor where host-guest contacts may take place. If these interactions occur stereoselectively, the CIS will be different for the two guest enantiomers (AS distinct from 0) giving possibly some insight into the chiral recognition mechanism. [Pg.52]

Crystal Chemistry of an Atropisomer Conformation, Chirality, Aromaticity AND Intermolecular Interactions ofDiphenylguanidine... [Pg.103]

Cyclic hexapeptides with alternating chirality (ldldld) prefer a C3 symmetric structure (three y-turns) 311 For symmetry reasons six y-turns (three above and three below the ring plane) can also be adopted, although this structure is difficult to prove and to distinguish because of the rapid flip-flop between two structures each with three y-turns 311 These types of structures lead to self-organization by strong intermolecular interactions into nanotubes (see Section 6.8.6.1). [Pg.481]

The Cotton effects may be classified into three types168 those arising from chirally perturbed local achiral chromophores (ketones, /i.y-unsaturated ketones, double bonds, benzoates, aromatic compounds) those arising from inherently achiral chromophores, such as conjugated dienes or a,/3-unsaturated ketones those arising from interaction of the various electric transition moments when two or more chromophores which are chirally disposed are positioned nearby in space, intra- or intermolecularly (exciton chirality method)169. [Pg.429]

In Section 3 we turn to reactions which require at least equimolar amounts of chiral information for the induction of asymmetry in the products. The newly formed asymmetric center can be induced by either intramolecular or by intermolecular interactions. Having served its stereochemical purpose, the amino acid moiety may be destroyed so that it does not exist as a discrete entity in the product, although sections of it may survive. [Pg.183]


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Interaction chiral

Intermolecular interaction

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