Cholesterics solvents

Liquid crystals are classified into lyotropic and thermotropic crystals depending on the way in which the mesomorphic phase is generated. Lyotropic liquid-crystalline solvents are formed by addition of controlled amounts of polar solvents to certain amphiphilic compounds. Thermotropic liquid-crystalline solvents, simply obtained by temperature variations, can be further classified into nematic, smectic, and cholesteric solvents depending on the type of molecular order present. Liquid crystals are usually excellent solvents for other organic compounds. Nonmesomorphic solute molecules may be incorporated into liquid-crystalline solvents without destruction of the order prevailing in the liquid-crystalline matrix (Michl and Thulstrup, 1986). Ordered solvent phases such as liquid crystals have also been used as reaction media, particularly for photochemical reactions (Nakano and Hirata, 1982). 

Our spectroscopic studies of BN in mixture B and in hexane support our contention that ground state conformers are forced by cholesteric mesophases toward extremes of 0 (i.e., closer to 0° or 180° than in hexane solvent). As the two naphthyl groups become more coplanar, their u-overlap increases. Consequently, the 0-0 transitions in absorption (and excitation) occur at longer wavelengths (lower energies) (43). For the same reasons, the cholesteric solvent compresses excited singlets of BN, causing their fluorescence spectra to be red-shifted with respect to those in hexane. 

Resolution attempts in cholesteric phases. Hie body of data collected to date clearly Indicates that unless specific solute-solvent Interactions occur, the stereochemistry of reactions will be little affected by chiral solvents, whether they be macrosco-pically ordered or isotropic (48-50). In fact, the low optical activity In products from irradiations in cholesteric solvents may arise from the ability of a chiral mesophase to produce circularly polarized light from normal incident radiation (51). 

Fig. 6. Cartoon representation of diffuslonal pathways by which the head and tail of PnP can collide to form efficiently an Intramolecular excimer. The double headed arrow denotes the cholesteric solvent director(40). [Reprinted with permission of the American Chemical Society.]...

Even within the experiments summarized here, several Important points need clarification. For example, the nature of PnP solubilization in mixed cholesteric solvents, which may be responsible for several dramatic effects discussed above, remains obscure. Also, the approach of Slsldo, to append a... 

Another example (which up to now seems very difficult to achieve) is based on chains dissolved in a cholesteric phase. This is a liquid where the molecules locally have one direction of alignment but where this direction has a helical twist in space. If we start with chains which are not optically active, crosslink them by an optically inactive agent, and then wash out the cholesteric solvent (replacing it by an achiral solvent), we should obtain a gel which has an optical rotatory power (a memory of its preparative state) although all its components do not distinguish right from left. ... 

However, recent reports in the literature seem to confirm the possibility of obtaining asymmetric induction, even if modest, by using cholesteric solvents(29,30). 

Reinitzer discovered liquid crystallinity in 1888 the so-called fourth state of matter.4 Liquid crystalline molecules combine the properties of mobility of liquids and orientational order of crystals. This phenomenon results from the anisotropy in the molecules from which the liquid crystals are built. Different factors may govern this anisotropy, for example, the presence of polar and apolar parts in the molecule, the fact that it contains flexible and rigid parts, or often a combination of both. Liquid crystals may be thermotropic, being a state of matter in between the solid and the liquid phase, or they may be lyotropic, that is, ordering induced by the solvent. In the latter case the solvent usually solvates a certain part of the molecule while the other part of the molecule helps induce aggregation, leading to mesoscopic assemblies. The first thermotropic mesophase discovered was a chiral nematic or cholesteric phase (N )4 named after the fact that it was observed in a cholesterol derivative. In hindsight, one can conclude that this was not the simplest mesophase possible. In fact, this mesophase is chiral, since the molecules are ordered in... 

Several natural10 and synthetic (e.g., polyisocyanates11) polymers form lyotropic cholesterics with the appropriate solvent also micellar systems formed by amphiphilic molecules and water, if chirality is introduced by either using a chiral amphiphile or adding a chiral dopant, can give cholesteric phases.12... 

Several natural and synthetic helical macromolecules such as DNA, polypeptides, and polyisocyanates form, in the appropriate solvent, cholesteric meso-phases. Also self-assembled supramolecular systems formed by guanosine derivatives 2 and 3 (G-wires), which are essentially four-stranded helices (Figure 7.8), behave in a similar way.35... 

From a cholesteric induction experiment, one can obtain chiral information on the induced cholesteric (namely, pitch and handedness) and therefore the helical twisting power of the dopant in that solvent (at a certain temperature). If a model or molecular theory relating molecular chirality to mesophase chirality is available, one can infer stereochemical information about the dopant (absolute configuration, preferred conformation). 

As mentioned in the introduction, the first empirical correlation between the absolute configuration of dopants and the handedness of induced cholesterics was proposed in 1975.20 The first attempt to find a general correlation was a few years later Krabbe et al.58 related the sense of the cholesteric to a stereochemical descriptor of the dopant based on the effective volume of the substituents and listed many compounds following this rule. However, exceptions were described at that time,59 and, furthermore, this approach neglects the role of the structure of the nematic solvent in determining the sense of the cholesteric. It is well known that chiral compounds may induce cholesterics of opposite handedness in different nematics.60,61... 

These results allowed the proposal, at the beginning of the 1980s, of a different molecular model for cholesteric induction 65,66 This model is sketched in Figure 7.15 in the case when both nematic host and chiral guest have a biaryl structure. Nematic molecules exist in chiral enantiomorphic conformations of opposite helicity in fast interconversion. The chiral dopant has a well-defined helicity (M in Figure 7.15) and stabilizes the homochiral conformation of the solvent In this way, the M chirality is transferred from the dopant to the near molecule of the solvent and from this to the next near one and so on. This... 

In the held of thermotropic cholesterics, the most promising approach seems to be that reported by Nordio and Ferrarini22 23 for calculating helical twisting powers. It allows one to tackle real molecules with rather complex structures and to describe them in detail. The model is currently being extended to include a better description of nematic solvents and specific solute-solvent interactions. Once tested also for conformationally mobile molecules, this model could allow the prediction of the handedness of single-component cholesterics, and, in the held of induced cholesterics, very interesting information on solute molecules could be obtained. 

The study of mesophases of cellulose and cellulose derivatives is an active field which has expanded rapidly since the initial observation of liquid crystms of hydroxy-propyl cellulose in 1976. There are two areas that warrant turther investigation recent observations regarding the influence of solvent and/or substituents on the cholesteric helicoidal twist await a theoretical explanation there is a lack of careful studies to permit a theoretical treatment of the behavior of ordered celltdose phases. To date, no applications have been developea where the unusual properties of cellulose derivatives are utilized. 

Solvent viscosity vs, concentration plots for cellulose dissolved in TFA-CH2CI2 (70/30, v/v) do not exhibit a maximum (1I,S1) in contrast to the typicid behavior of polymer liquid crystal solutions. This same behavior is exhibited by other cellulose-solvent systems (52,fiQ). Conio et al. (59) si gest that due to the close proximity of the cholesteric mesophase to its solubility limit, it is only observed in a metastable condition. 

Solutions of cellulose in NH3/NH4SCN (27 73 w/w) are liquid crystalline at concentrations from 10-16% (w/w) depending on the cellulose molecular weight (64). Optical rotations of the solutions indicate the mesophase is cholesteric with a left-handed twist. The solvent does not react with cellulose. Recently, Yang (60) foimd that cellulose (D.P. 210) formed a mesophase at 3.5% (w/w) concentration at a NH3/NH4SCN of 30 70 (w/w). 

Werbowyj and Gray (79) examined the relationships between the cholesteric pitch and optical properties of HPC in water, CH3COOH and CH3OH. The reciproc pitch varied as the third power of the HPC concentration. Optical rotatory dispersion results show HPC has a right-handed superhelicoidal structure regardless of structure. As will be discussea below, a change in solvent can reverse the handedness of other cellulose derivatives. 

Navard and Haudin studied the thermal behavior of HPC mesophases (87.88) as did Werbowyj and Gray (2), Seurin et al. (Sp and, as noted above, Conio et al. (43). In summary, HjPC in H2O exhibits a unique phase behavior characterized by reversible transitions at constant temperatures above 40 C and at constant compositions when the HPC concentration is above ca. 40%. A definitive paper has been recently published by Fortin and Charlet ( who studied the phase-separation temperatures for aqueous solutions of HPC using carefully fractionated HPC samples. They showed the polymer-solvent interaction differs in tiie cholesteric phase (ordered molecular arrangement) from that in the isotropic phase (random molecular arrangement). 

Vo and Zugenmaier (105) determined the pitch of cellulose tricarbanilate (CTC, D.P. = 100) in 2-pentanone and methyl ethyl ketone (MEK) and ethyl cellulose (EC) in glacial acetic acid as a function of temperature, concentration, solvent, and degree of polymerization. The pitch of the helicoidal structure of CTC/MEK and CTC/2-pentanone is right-handed but EC in glacial acetic acid is left-handed. This is the first report that the substituent will influence the sense of the cholesteric superhelicoidal structure. 

As compared to the cholesteric LC, the lyotropic LC consists of two or more components that exhibit liquid-crystalline properties (dependent on concentration, temperature, and pressure). In the lyotropic phases, solvent molecules fill the space around the compounds (such as soaps) to provide fluidity to the system. In contrast to thermotropic liquid crystals, these lyotropics have another degree of freedom of concentration that enables them to induce a variety of different phases. A typical lyotropic liquid crystal is surfactant-water-long-chain alcohol. 

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