In situ 13C solid-state polarization transfer NMR to follow starch transformations in food

Convenience food products tend to alter their quality and texture while stored. Texture-giving food components are often starch-rich ingredients, such as pasta or rice. Starch transforms depending on time, temperature and water content, which alters the properties of products. Monitoring these transformations, which are associated with a change in mobility of the starch chain segments, could optimize the quality of food products containing multiple ingredients. In order to do so, we applied a simple and efficient in situ ¹³C solid-state magic angle spinning (MAS) NMR approach, based on two different polarization transfer schemes, cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT). The efficiency of the CP and INEPT transfer depends strongly on the mobility of chain segments—the time scale of reorientation of the CH-bond and the order parameter. Rigid crystalline or amorphous starch chains give rise to CP peaks, whereas mobile gelatinized starch chains appear as INEPT peaks. Comparing ¹³C solid-state MAS NMR experiments based on CP and INEPT allows insight into the progress of gelatinization, and other starch transformations, by reporting on both rigid and mobile starch chains simultaneously with atomic resolution by the ¹³C chemical shift. In conjunction with ¹H solid-state MAS NMR, complementary information about other food components present at low concentration, such as lipids and protein, can be obtained. We demonstrate our approach on starch-based products and commercial pasta as a function of temperature and storage.     

Liquid crystals from hydrogen-bonded amphiphiles

Liquid crystals originating from hydrogen-bonded amphiphiles will be discussed, highlighting the structural features of the amphiphilic components that lead to supramolecular systems exhibiting liquid crystalline character. Liquid crystalline phases derived from two types of hydrogen-bonded amphiphiles will be presented: (a) liquid crystalline phases originating from multihydroxylated amphiphiles; and (b) liquid crystalline phases resulting from combined hydrogen bonding and ionic interactions.     

Nonionic diethanolamide amphiphiles with saturated hydrocarbon chains: Neat crystalline and lyotropic liquid crystalline phase behavior

The solid state and lyotropic phase behavior of a series of nonionic diethanolamide amphiphiles with increasing saturated hydrocarbon chain length (lauroyl, myristoyl, palmitoyl, and stearoyl) has been examined. All four saturated diethanolamide amphiphiles form a crystalline solid with two or three different polymorphic crystalline forms at room temperature. Melting points and associated enthalpies for these four amphiphiles increased with increasing chain length. Approximate partial binary phase diagrams have been constructed for each amphiphile/water system by combining Cross-Polarized Optical Microscopy (POM) and Small-Angle X-ray Scattering (SAXS) results. In the presence of water, all four diethanolamides form an L(α) phase, between 10% and 50% water content, and an L(2) phase with decreasing hydration and increasing temperature. In addition to the L(α) and L(2) phases, the shorter chain diethanolamide amphiphiles (lauroyl and myristoyl) also display a normal micellar phase (L(1)) at higher water contents, occurring to lower temperatures than the L(α) phase. By examining the effect of subtle molecular changes on both neat and lyotropic phase behavior, amphiphiles can be designed with properties tailored to a desired application.     

Amphiphilic Comb‐Like Poly(oxyethylene) and Its Complexes with LiClO4: Synthesis and Mesomorphic Behavior

Summary: We prepared an amphiphilic, comb‐like poly(oxyethylene) containing decyl‐tri(oxyethylene) amphiphiles in the side chain using a polymer analogous reaction to obtain a novel nonionic amphiphilic polymeric system with high molecular weight. The amphiphilic comb‐like poly(oxyethylene) itself only showed a side‐chain crystalline phase below its melting temperature of −31 °C. When the polymer was mixed with lithium perchlorate, a smectic liquid‐crystalline phase appeared. The ordered phases of the polymer and the polymer mixture were studied by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction.

POM image (200 X) of D3OTP1 at room temperature.     

Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes

A series of chelating amphiphiles and their gadolinium (Gd(iii)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.     

Ordered 2-D and 3-D nanostructured amphiphile self-assembly materials stable in excess solvent

Amphiphile lyotropic liquid crystalline self-assembly materials are being used for a diverse range of applications. Historically, the most studied lyotropic liquid crystalline phase is probably the one-dimensional (1-D) lamellar phase, which has been employed as a model system for biomembranes and for drug delivery applications. In recent years, the structurally more complex 2-D and 3-D ordered lyotropic liquid crystalline phases, of which reversed hexagonal (H(2)) and reversed cubic phases (v(2)) are two prominent examples, have received growing interest. As is the case for the lamellar phase, these phases are frequently stable in excess water, which facilitates the preparation of nanoparticle dispersions and makes them suitable candidates for the encapsulation and controlled release of drugs. Integral membrane protein crystallization media and templates for the synthesis of inorganic nanostructured materials are other applications for 2-D and 3-D amphiphile self-assembly materials. The number of amphiphiles identified as forming nanostructured reversed phases stable in excess solvent is rapidly growing. In this article, different classes of amphiphiles that form reversed phases in excess solvent are reviewed, with an emphasis on linking phase behavior to amphiphile structure. The different amphiphile classes include: ethylene oxide-, monoacylglycerol-, glycolipid-, phosphatidylethanolamine-, and urea-based amphiphiles.     

Phase behavior and polymerization of lyotropic phases. II. A series of polymerizable amphiphiles with systematically varied critical packing parameters

A group of polymerizable amphiphiles, with their critical packing parameters systematically varied, were studied with respect to the phase behavior and immobilization of their lyotropic liquid‐crystalline phase structures. Small‐angle X‐ray scattering and polarized light microscopy were used to study their liquid‐crystalline phases before and after photopolymerization. The liquid crystallinity of the amphiphiles depended on the contents of both oil and water in the ternary systems. Through photopolymerization, hexagonal phases could generally be immobilized, with the structural order reduced to various degrees. However, the cubic phases evolved with polymerization into another structural pattern, which was possibly related to the lamellar structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5887–5897, 2006     

Evaluation of microstructural features of a new polymeric organic stationary phase grafted on silica surface: A paradigm of characterization of HPLC-stationary phases by a combination of suspension-state H NMR and solid-state C-CP/MAS-NMR

Silica-supported poly(octadecylacrylate) (Sil-ODA_n), polymeric octadecylsilyl silica (polymeric ODS), and monomeric octadecylsilyl silica (monomeric ODS) were studied by a combination of suspension-state ¹H NMR and solid-state ¹³C CP/MAS-NMR to probe the mechanisms underlying their functions as stationary phases for RP-HPLC. Sil-ODA_n, with a strong temperature dependent separation behaviour showed correspondent temperature dependent manifestations in both suspension-state ¹H NMR and solid-state ¹³C CP/MAS-NMR experiments. With a gradual increase in temperature, intensity of proton signals (¹H NMR) of octadecyl moieties (mainly methylene groups) rose dramatically. This dramatic rise was at the same temperature of an endothermic peak detectable in its DSC thermogram indicating a relatively complete solid to liquid phase transition. In addition temperature dependencies of the ratio of trans to gauche conformed well to temperature dependencies of the separation factor between naphthacene and triphenylene (as a simple indicator of shape selectivity). Therefore NMR spectra of Sil-ODA_n were used as a reference for ascertaining percentage of octadecyl moieties of liquid type mobility in the two other stationary phases. Using this method we determined percentage of liquid phase in polymeric ODS and monomeric ODS at various temperatures. We suggest a combination of suspension-state ¹H NMR and solid-state ¹³C CP/MAS-NMR for structure-dynamic characterization of various kinds of hydrocarbon chains grafted onto the silica particles.     

Diversifying the solid state and lyotropic phase behavior of nonionic urea-based surfactants

The solid state and lyotropic phase behavior of 10 new nonionic urea-based surfactants has been characterized. The strong homo-urea interaction, which can prevent urea surfactants from forming lyotropic liquid crystalline phases, has been ameliorated through the use of isoprenoid hydrocarbon tails such as phytanyl (3,7,11,15-tetramethyl-hexadecyl) and hexahydrofarnesyl (3,7,11-trimethyl-dodecyl) or the oleyl chain (cis-octadec-9-enyl). Additionally, the urea head group was modified by attaching either a hydroxy alkyl (short chain alcohol) moiety to one of the nitrogens of the urea or by effectively "doubling" the urea head group by replacing it with a biuret head group. The solid state phase behavior, including the liquid crystal-isotropic liquid, polymorphic, and glass transitions, is interpreted in terms of molecular geometries and probable hydrogen-bonding interactions. Four of the modified urea surfactants displayed ordered lyotropic liquid crystalline phases that were stable in excess water at both room and physiological temperatures, namely, 1-(2-hydroxyethyl)-1-oleyl urea (oleyl 1,1-HEU) with a 1D lamellar phase (Lalpha), 1-(2-hydroxyethyl)-3-phytanyl urea (Phyt 1,3-HEU) with a 2D inverse hexagonal phase (HII), and 1-(2-hydroxyethyl)-1-phytanyl urea (Phyt 1,1-HEU) and 1-(2-hydroxyethyl)-3-hexahydrofarnesyl urea (Hfarn 1,3-HEU) with a 3D bicontinuous cubic phase (QII). Phyt 1,1-HEU exhibited rich mesomorphism (QII1, QII2, Lalpha, LU, and HII), as did one other surfactant, oleyl 1,3-HEU (QII1, QII2, Lalpha, LU, and HII), in the study group. LU is an unusual phase which is mobile and isotropic but possesses shear birefringence, and has been very tentatively assigned as an inverse sponge phase. Three other surfactants exhibited a single lyotropic liquid crystalline phase, either Lalpha or HII, at temperatures >50 degrees C. The 10 new surfactants are compared with other recently reported nonionic urea surfactants. Structure-property correlations are examined for this novel group of self-assembling amphiphiles.     

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.     

Phase behavior of 1-alkylpyridinium octane-1-sulfonates. effect of the 1-alkylpyridinium counterion size

The temperature-versus-composition phase diagrams of eight different 1-alkylpyridinium octane-1-sulfonates (APOSs) in water were studied by 1H NMR, 2H NMR, pulsed gradient spin-echo NMR, small-angle X-ray diffraction, differential scanning calorimetry, surface tension and conductivity measurements, and polarizing microscopy. The number of carbons (n(c)) in the hydrocarbon chain of the pyridinium counterions was varied from n(c) = 1 to n(c) = 8 to study how the phase behavior of the APOS/2H2O systems was affected by a change in the chain length of the counterion. The sodium octane-1-sulfonate (NaOS)/water system was used as a reference. This system formed an isotropic micellar solution (L1) phase and a normal hexagonal (H(I)) phase. All APOSs were readily soluble in water and formed L1 phases. The surface tension above the critical micelle concentration for n(c) between 1 and 3 was higher than that for NaOS, and it decreased steadily for the different APOSs with increasing chain length. The area per molecule at the air/solution interfaces was rather constant at 68 A2 for n(c) between 1 and 7. For 1-octylpyridinium octane-1-sulfonate (OPOS), it was about 5 A2 smaller, which was just outside the estimated error. However, the smallest area was obtained for NaOS. At higher surfactant concentrations, liquid crystalline phases formed. Both cubic and H(I) phases were found for n(c) = 1 and 2, while for n(c) between 3 and 5 only an H(I) phase was observed. H(I) and lamellar liquid crystalline (Lalpha) phases formed for n(c) = 6 and 7. The only liquid crystalline phase found in the OPOS system was a Lalpha phase. The NaOS H(I) phase was the only liquid crystalline phase that showed a linear relation between the 2H2O NMR quadrupolar splitting (deltaW) and Xsurf/X(W), where Xsurf and X(W) are the mole fractions of surfactant and water. The OPOS lamellae were found to be much thinner than expected, indicating a defect lamellar structure. This was further supported by the behavior of the quadrupolar splitting ofdeuterated OPOS. The anomalous behaviors of the 2H2O NMR quadrupolar splitting observed in the Lalpha phases of 1-heptylpyridinium octane-1-sulfonate and OPOS were interpreted in terms of changes in the population of the water molecules residing in different sites combined with a continuous rearrangement of the lamellae surface with the possible development of holes. The appearances of the phase diagrams were discussed in terms of surfactant molecular geometry and the packing of the amphiphiles in the aggregates formed.     

Chemistry of Synthetic Bilayer Membranes

The preparation of bilayer membranes from synthetic dialkyl amphiphiles is described. According to the electron microscopic observation, the bilayer structure similar to that of biomembranes is formed spontaneously when dialkyldimethyl-ammonium bromides with C₁₀-C₂₀ alkyl groups are dispersed in water by sonication. The line broadening in the NMR spectrum strongly suggests that these synthetic bilayers constitute liquid crystalline or solid phases. The hydrophilic head group may be sulfonium and modified ammonium moieties. The bilayer assembly is also formed from dialkyl amphiphiles with anionic head groups: (phosphate, sulfonate, and carboxylate), from nonionic dialkyl amphiphiles (oligomeric ethylene oxide) moiety) and from zwitterionic dialkyl amphiphiles. These bilayers incorporate equimolar cholesterol fairly readily. The redistribution of catalyst (a cholesterol derivative) and substrate (p-nitrophenyl palmitate) molecules is very slow when they are tightly bound to the aggregate. The intravesicle reaction is much faster than the intervesicle counterpart in the case of the di-dodecyldimethylammonium bromide vesicle.     

A study of molecular dynamics and phase transitions in solid MBBA

Abstract

The solid state polymorphism of liquid crystalline MBBA was investigated by temperature dependent NMR spin-lattice relaxation time measurements. The sensitivity of the method could be utilized because the correlation time of the measurement is in the correlation time region of molecular motion. Motional correlation time and activation energy values were determined and the results show some interesting changes between the different solid phases. Non-trivial variation in the end-chain rotational motion in two crystalline phases has been observed. Conclusions were drawn on the relationship between rotational molecular dynamics, intermolecular order and phase transitions.     

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 °C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 ? following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L(2) phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L(α)) at room temperature and up to ～ 40 °C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q(II)(D)) and gyroid (Q(II)(G)) bicontinuous cubic phases in addition to an L(α) phase.     

Amphotropic liquid crystals

The liquid crystalline state is a fundamental organization of matter, which combines order and mobility on a molecular, supramolecular and macroscopic level. In many cases the molecules can show both thermotropic and lyotropic liquid-crystalline (LC) phases, which is described as amphotropic behavior. Block-copolymers, polyhydroxy amphiphiles, disc-like, rod-like, polycatenar and banana-shaped LC molecules are discussed with respect to their amphotropic behavior with specific and non-specific solvents. The interactions of salts with polyether chains, leading to halotropic mesophases, and the interaction of aromatic electron acceptor molecules with electron-rich aromatic molecular parts are discussed in relation to lyotropic mesomorphism induced by classical solvent molecules. Polyphilic amphotropic materials showing more complex mesophase morphology and amphiphiles showing a hierarchical order of different levels of order are pointed out as future directions.     

Lyotropic liquid crystalline phase behaviour of a monomeric and a polymeric monosaccharide amphiphile in aqueous solution

Monomeric and polymeric amphiphiles were synthesized which exhibit lyotropic liquid crystalline phases in aqueous solution. The hydrophobic group of the monomeric surfactant is a dodecane-group esterified with acrylic acid. The hydrophilic unit is a monosaccharide derivative. By radical polymerization the monomer (N-D(-)-gluco-N-methyl-(12-acryloyloxy)-dodecane-l-amide) is converted into the corresponding polymeric surfactant. The monomer as well as the polymer exhibit a lyotropic 1.c. phase of lamellar structure. Owing to the polymerization the regime of the lamellar phase is greatly enlarged for the polymer, compared to the monomeric sufactant. These results confirm earlier investigations on non-ionic ethylene-glycol surfactants.     

Control of molecular structure in the generation of highly luminescent liquid crystalline perylenebisimide derivatives: synthesis, liquid crystalline and photophysical properties

We report here, for the first time, the role of the molecular design on the liquid crystalline and solid-state photoluminescent properties of soluble and thermally stable liquid crystalline perylenebisimide derivatives. A new series of perylenebisimides were designed and developed for this purpose by adopting the stoichiometry-control approach, and amine-, hydroxyl-, ester-, and amide-functionalized molecules were synthesized. Various types of spacers with different lengths (C(2) to C(12)), types (linear, cyclohexyl, and tricyclodecane), and end-capped by phenyl or tridodecyloxy gallic units were introduced in the perylenebisimide core. The molecules were completely characterized by NMR, FT-IR, SEC, and MALDI-TOF mass techniques. Thermal analysis revealed that the perylenebisimide derivatives were thermotropic liquid crystalline, and threadlike nematic phases were observed under a polarizing light microscope. The spacer length and the rigidity of the spacers play a major role in the liquid crystalline properties of the materials. In phenyl systems, the C(6) chain with ester- and the C(12) chain with amide-end-capped molecules showed a nematic phase, whereas the C(6) chain with an amide end cap and their cyclic and tricyclic counterparts did not show any LC property. The introduction of a tridodecyloxy gallic unit induced the LC property in C(12) and the cyclohexyl system; however, it failed to do so in the tricyclodecane molecule. The absorption properties of the molecules were almost unchanged by the structural variation; however, the emission quantum yield in solution and photoluminescent (PL) intensity in the solid state were significantly different. Though the gallic unit induced liquid crystallinity in the perylenebisimide core, the quantum yield and PL intensity are 4-5 times less compared to those of the simple phenyl-capped liquid crystalline system. Among the various types of spacers, the tricyclodecane induced strong molecular aggregates via pi-stacking, which in turn increased the rigidity of the entire perylenebisimide core, resulting in the absence of liquid crystallinity and low luminescence compared to their linear and cyclohexyl analogues. The molecular aggregates were very stable even at very dilute concentration and also at high temperatures. The aggregates disappeared immediately upon addition of trifluoroacetic acid, thus confirming the strong hydrogen bonding in the aggregated states. In a nutshell, the present report demonstrates the importance of molecular design for introducing liquid crystalline phases in perylenebisimides and also the development of novel highly luminescent n-type pi-conjugated material for application in optoelectronics.     

Nonionic diethanolamide amphiphiles with unsaturated C18 hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behavior

The neat and lyotropic liquid crystalline phase behavior of three nonionic diethanolamide amphiphiles with C18 hydrocarbon chains containing one, two or three unsaturated bonds has been examined. This has allowed the effect of degree of unsaturation on the phase behavior of diethanolamide amphiphiles to be investigated. Neat linoleoyl and linolenoyl diethanolamide undergo a transition from a glassy liquid crystal to a liquid crystal at ～-85 °C, while neat oleoyl diethanolamide undergoes a transition at ～-60 °C to a liquid crystalline material before re-crystallizing at -34 °C. Oleoyl diethanolamide then undergoes a third transition from a crystalline phase to a smectic liquid crystalline phase at ～5 °C. In the absence of water, the transition temperature from a smectic liquid crystal to an isotropic liquid decreases with increasing unsaturation. The addition of water results in the formation of a lamellar phase (L(α)) for all three amphiphiles. The lamellar phase is stable under excess water conditions up to temperatures of at least 70 °C. Approximate partial binary amphiphile-water phase diagrams generated for the three unsaturated C18 amphiphiles indicate that the excess water point for each amphiphile occurs at ～60% (w/w) amphiphile.     

Mesomorphic properties of 5boSOMH from new three rings thiobenzoate series

Phase polymorphism of a novel chiral liquid crystalline compound (S)-(+)-4-{4-(4-n-pentylbicyclo[2,2,2]octancarbonylthio)benzoyloxy}benzoate 1-methylheptyl (in short: 5boSOMH) was examined with three complementary methods: Differential Scanning Calorimetry (DSC), Polarized Light Optical Microscopy (POM) and Transmitted Light Intensity (TLI). X-Ray diffraction was used to learn about molecular arrangement in ordered phases. 5boSOMH has two enantiotropic phases: SmB* and SmA*, and exhibits solid phase polymorphism.     

Phase diagram and dielectric relaxation studies of n-octyl-isothiocyanato-biphenyl (8BT) in the crystalline E phase under high pressure

The pressure-temperature phase diagram of n-octyl-isothiocyanato-biphenyl (8BT) in the pressure range up to 250 MPa (2.5 kbar) and the temperature range 250-400 K was established with the aid of DTA. At 1 atm the substance exhibits exclusively CrE polymorphism. At pressures above 190 MPa, the clearing line splits showing an additional phase which is not yet identified. Dielectric relaxation measurements on the CrE phase of 8BT were performed in the pressure range 0.1-120 MPa and the temperature range 304-345 K. A Debye-type relaxation process was observed in the frequency range 100 Hz-1 MHz. The longitudinal relaxation time τ, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature, yielding the activation volume, Δ^# V = RT(? ln τ/?p)_T, and activation enthalpy, Δ^# H = R(? ln τ/? T^-1)_p, respectively. The results are compared with analogous data obtained recently for similar compounds having other liquid crystalline phases (N, SmA).