Behavior of liquid crystals confined to mesoporous materials as studied by 13C NMR spectroscopy of methyl iodide and methane as probe molecules

The behavior of thermotropic nematic liquid crystals (LCs) Merck Phase 4 and ZLI 1115 confined to mesoporous controlled pore glass materials was investigated using 13C nuclear magnetic resonance spectroscopy of probe molecules methyl iodide and methane. The average pore diameters of the materials varied from 81 to 375 A, and the temperature series measurements were performed on solid, nematic, and isotropic phases of bulk LCs. Chemical shift, intensity, and line shape of the resonance signals in the spectra contain lots of information about the effect of confinement on the state of the LCs. The line shape of the 13C resonances of the CH3I molecules in LCs confined into the pores was observed to be even more sensitive to the LC orientation distribution than, for example, that of 2H spectra of deuterated LCs or 129Xe spectra of dissolved xenon gas. The effect of the magnetic field on the orientation of LC molecules inside the pores was examined in four different magnetic fields varying from 4.70 to 11.74 T. The magnetic field was found to have significant effect on the orientation of LC molecules in the largest pores and close to the nematic-isotropic phase transition temperature. The theoretical model of shielding of noble gases dissolved in LCs based on pairwise additivity approximation was utilized in the analysis of CH4 spectra. For the first time, a first-order nematic-isotropic phase transition was detected to take place inside such restrictive hosts. In the larger pores a few degrees below the nematic-isotropic phase transition of bulk LC the 13C quartet of CH3I changes as a powder pattern. Results are compared to those derived from 129Xe NMR measurements of xenon gas in similar environments.     

2D 129Xe EXSY of xenon atoms in a thermotropic liquid crystal confined to a controlled-pore glass

Two-dimensional (129)Xe exchange spectroscopy (EXSY) NMR measurements are presented for xenon atoms dissolved in a thermotropic nematic Liquid Crystal (LC), Merck Phase 4, confined to a mesoporous Controlled-Pore Glass (CPG) material with an average pore diameter of 81 A. Experiments were carried out as a function of mixing time at two different temperatures in which Phase 4 appears in nematic and isotropic phases. The exchange rate constants of xenon atoms between two different sites were determined utilizing the intensities of diagonal and off-diagonal signals measured in the EXSY spectra. In the studied system, the sites are: (a) xenon dissolved in the bulk LC between the CPG particles; and (b) xenon in the LC confined inside the pores. The diffusion rate of xenon atoms between the various sites was observed to be very slow.     

Behavior of a thermotropic nematic liquid crystal confined to controlled pore glasses as studied by 129Xe NMR spectroscopy

The behavior of nematic liquid crystal (LC) Merck Phase 4 confined to controlled pore glass (CPG) materials was investigated using 129Xe nuclear magnetic resonance (NMR) spectroscopy of xenon gas dissolved in the LC. The average pore diameters of the materials varied from 81 to 2917 A, and the measurements were carried out within a wide temperature range (approximately 185-370 K). The spectra contain lots of information about the effect of confinement on the phase of the LC. The theoretical model of shielding of noble gases dissolved in liquid crystals on the basis of pairwise additivity approximation was applied to the analysis of the spectra. When pore diameter is small, smaller than approximately 150 A, xenon experiences on average an isotropic environment inside the pore, and no nematic-isotropic phase transition is observed. When the size is larger than approximately 150 A, nematic phase is observed, and the LC molecules are oriented along pore axis. The orientational order parameter of the LC, S, increases with increasing pore size. In the largest pores, the orientation of the molecules deviates from the pore axis direction to magnetic field direction, which implies that the size of the pores (approximately 3000 A) is close to magnetic coherence length. The decrease of magnetic coherence length with increasing temperature is clearly seen from the spectra. When the sample is cooled rapidly by immersing it in liquid nitrogen, xenon atoms do not squeeze out from the solid, as they do during gradual freezing, but they are occluded inside the solid lattice, and their chemical shift is very sensitive to crystal structure. This makes it possible to study the effect of confinement on the solid phases. According to the measured 129Xe NMR spectra, possibly three different solid phases are observed from bulk liquid crystal in the used temperature region. The same is also seen from the samples containing larger pores (pore size larger than approximately 500 A), and the solid-solid phase-transition temperatures are the same. However, no first-order solid-solid phase transitions are observed from the smaller pores. Melting point depression, that is, the depression of solid-nematic transition temperature observed from the pores as compared with that in bulk LC, is seen to be very sensitive to the pore size, and it can be used for the determination of pore size of an unknown material.     

Determination of polarity parameters for liquid crystals using solvatochromic method in anisotropic and isotropic phases

The use of liquid crystals (LCs) as anisotropic solvents is desired for various potential applications and usually for other organic and inorganic compounds. In this work, solvent polarity parameters are obtained using a spectroscopic method for four LCs with a range of high and low dielectric anisotropy (?ε). Solvatochromic polarity parameters for these LCs were defined via Kamlet–Abboud–Taft polarity functions characterizing different temperatures and phases, isotropic and anisotropic, and using the Reichardt’s dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio) phenolate standard probe. The investigated polarity parameters reveal the effects of LC media on the photo-physical behaviour of solute molecules in isotropic and anisotropic media. Subsequently, a new LC polarity parameter (Z_o) is introduced as an overall matrix anisotropy polarity parameter to characterize variation between isotropic and anisotropic phases. The values of Z_o are sorted from higher to lower dielectric anisotropies (?ε).     

The effect of surface polarity of glass on liquid crystal alignment

The effects of the surface polarity of a glass substrate on the orientation of nematic liquid crystals (LCs) were studied using the polarised optical microscope and Fourier-transform infrared spectroscopy. On the surface of oxygen plasma treated glass, a homeotropic alignment of LCs was induced for LCs with negative dielectric anisotropy. This suggests that vertical orientation of LCs could be induced on a polar glass substrate without using an LC alignment layer. Upon cooling towards the isotropic–nematic transition, E7 with positive dielectric anisotropy changes its LC arrangement to isotropic, homeotropic, planar orientations in order. The nematic LC anchoring transition of E7 was interpreted by considering the competition between van der Waals forces and dipole interactions that control the alignment of LC molecules on a polar glass surface.     

New highly anisotropic liquid crystal materials for high-frequency applications

We report on the developed liquid crystal (LC) compositions with large optical anisotropy and low melting point on the basis of synthesised quaterphenyl and quinquiphenyl LC compounds containing lateral substituents. Optical and dielectric anisotropies of synthesised compounds were studied to select the most optimal compounds for high-frequency applications. As a result of the research, base matrices with a wide range of the nematic phase were developed and their mesomorphic and physicochemical properties were investigated. Based on the experimental data, the influence of various fragments of molecules on the magnitude of permittivity in the high-frequency region, as well as on the loss tangent of LCs was established.     

Nuclear magnetic resonance shielding tensors calculated with kinetic energy density-dependent exchange-correlation functionals

Exchange-correlation functionals that depend on the non-interacting kinetic energy density (τ) break gauge invariance in the presence of a magnetic field. This yields incorrect results for molecular magnetic properties. We propose a simple generalization of the kinetic energy density that resolves this problem. Our modification is validated by computing NMR absolute isotropic shielding constants and shielding anisotropies with τ-dependent functionals for a representative set of molecules. The accuracy of τ-dependent approximations is found to surpass that of common generalized gradient approximations (GGA) and hybrid functionals for strongly deshielded nuclei.     

Proton magnetic shielding tensor in liquid water

The nuclear magnetic shielding tensor is a sensitive probe of the local electronic environment, providing information about molecular structure and intermolecular interactions. The magnetic shielding tensor of the water proton has been determined in hexagonal ice, but in liquid water, where the tensor is isotropically averaged by rapid molecular tumbling, only the trace of the tensor has been measured. We report here the first determination of the proton shielding anisotropy in liquid water, which, when combined with chemical shift data, yields the principal shielding components parallel (sigma(parallel)) and perpendicular (sigma(perpendicular)) to the O-H bond. We obtained the shielding anisotropy sigma(parallel)-sigma(perpendicular) by measuring the proton spin relaxation rate as a function of magnetic induction field in a water sample where dipole-dipole couplings are suppressed by H/D isotope dilution. The temperature dependence of the shielding components, determined from 0 to 80 degrees C, reflects vibrational averaging over a distribution of instantaneous hydrogen-bond geometries in the liquid and thus contains unique information about the temperature-dependent structure of liquid water. The temperature dependence of the shielding anisotropy is found to be 4 times stronger than that of the isotropic shielding. We analyze the liquid water shielding components in the light of previous NMR and theoretical results for vapor and ice. We show that a simple two-state model of water structure fails to give a consistent interpretation of the shielding data and we argue that a more detailed analysis is needed that quantitatively relates the shielding components to hydrogen bond geometry.     

Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

Recently, various techniques have been developed using photonic crystals. Liquid crystals (LC) confined in a nanodroplet mimicked photonic crystals, such as those of opal. Therefore, investigating the phase behaviour of LC molecules in nanodroplets is very important in the next-generation optical field. In this study, the chemical interaction between surfactants and LCs in nanodroplets is reproduced using a dissipative particle dynamics method. We identify the phase behaviour of LCs and investigate how the chemical interaction affect on the orientation of LCs. In particular, by adding surfactant molecules, various morphological behaviours were observed in the LC nanodroplet. The phase transition temperature varied depending on R_ND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on R_ND. Our simulation offers a theoretical guide to control morphologies of self-assembled LCs inside a nanodroplet, a novel system that may find applications in nanofluidic devices or in photonic crystal technology.     

Local high-density distributions of phospholipids induced by the nucleation and growth of smectic liquid crystals at the interface

Amphiphilic molecules adsorbed at the interface could control the orientation of liquid crystals (LCs) while LCs in turn could influence the distributions of amphiphilic molecules. The studies on the interactions between liquid crystals and amphiphilic molecules at the interface are important for the development of molecular sensors. In this paper, we demonstrate that the development of smectic LC ordering from isotropic at the LC/water interface could induce local high-density distributions of amphiphilic phospholipids. Mixtures of liquid crystals and phospholipids in chloroform are first emulsified in water. By fluorescently labeling the phospholipids adsorbed at the interface, their distributions are visualized under fluorescent confocal microscope. Interestingly, local high-density distributions of phospholipids showing a high fluorescent intensity are observed on the surface of LC droplets. Investigations on the correlation between phospholipid density, surface tension and smectic LC ordering suggest that when domains of smectic LC layers nucleate and grow from isotropic at the LC/water interface as chloroform slowly evaporates at room temperature, phospholipids transition from liquid-expanded to liquid-condensed phases in response to the smectic ordering, which induces a higher surface tension at the interface. The results will provide an important insight into the interactions between liquid crystals and amphiphilic molecules at the interface.     

Swelling behaviour of poly(butadiene) gels in liquid crystal solvents

The swelling behaviour of poly(butadiene) gels in four different nematogenic liquid crystalline (LC) solvents has been investigated as a function of temperature (T). Microscopy with crossed polarizers reveals that the nematic to isotropic phase transition temperature of the LC solvents inside the gels (T_NI ^g) is slightly lower than that of the surrounding pure LC solvents (T_NI ^o), but the degrees of depression in T_NI ^g in each system are comparable regardless of the considerable differences in the degrees of equilibrium swelling (Q) at T_NI ^g between the various systems. In general, Q in the isotropic phase is larger than that in the nematic phase, but a unique swelling behaviour of the gel is found in the vicinity of T_NI due to the phase transition of the LC solvents. Q remains constant in the temperature range of T_NI ^g ≤ T ≤ T_NI ^o in which the phases of the LCs outside or inside the domain of the gels are different, namely, nematic and isotropic phase, respectively. In addition, a finite abrupt (discontinuous-like) change in Q is observed at around T_NI. The gels swollen in the LCs, having an ability to interact with the crosslinking points via hydrogen bonding, show a significant thermal hysteresis for the temperature dependence of Q in the vicinity of T_NI, while no discernible thermal hysteresis is observed for the gels in the LCs incapable of forming hydrogen bonds.     

A comparison of quantum chemical models for calculating NMR shielding parameters in peptides: mixed basis set and ONIOM methods combined with a complete basis set extrapolation

This article compares several quantum mechanical approaches to the computation of chemical shielding tensors in peptide fragments. First, we describe the effects of basis set quality up to the complete basis set (CBS) limit and level of theory (HF, MP2, and DFT) for four different atoms in trans N-methylacetamide. For both isotropic shielding and shielding anisotropy, the MP2 results in the CBS limit show the best agreement with experiment. The HF values show quite a different tendency to MP2, and even in the CBS limit they are far from experiment for not only the isotropic shielding of carbonyl carbon but also most shielding anisotropies. In most cases, the DFT values differ systematically from MP2, and small basis-set (double- or triple-zeta) results are often fortuitously in better agreement with the experiment than the CBS ones. Second, we compare the mixed basis set and ONIOM methods, combined with CBS extrapolation, for chemical shielding calculations at a DFT level using various model peptides. From the results, it is shown that the mixed basis set method provides better results than ONIOM, compared to CBS calculations using the nonpartitioned full systems. The information studied here will be useful in guiding the selection of proper quantum chemical models, which are in a tradeoff between accuracy and cost, for shielding studies of peptides and proteins.     

NMR nuclear magnetic shielding anisotropy of linear molecules within the linear response within the elimination of the small component approach

The influence of the spin-Zeeman (SZ) operator in the evaluation of the spin-orbit effect on the nuclear magnetic shielding tensor in the context of the linear response within the elimination of the small component approach is critically discussed. It is shown that such term yields no contribution to the isotropic nuclear magnetic shielding constant, but it may be of great importance in the determination of individual tensor components, and particularly of the tensor anisotropy. In particular, an interesting relation between the SZ and orbital Zeeman contributions to the spin-orbit effect for the case of linear molecules is shown to hold. Numerical examples for the BrH, IH, and XeF(2) molecules are presented which show that, provided the SZ term is taken into account, results of the individual shielding tensor components and the tensor anisotropy are in good agreement with those obtained by other theoretical methods, and particularly by the Dirac-Hartree-Fock approach.     

Carbon-13 NMR shielding in the twenty common amino acids: comparisons with experimental results in proteins

We have used ab initio quantum chemical techniques to compute the (13)C(alpha) and (13)C(beta) shielding surfaces for the 14 amino acids not previously investigated (R. H. Havlin et al., J. Am. Chem. Soc. 1997, 119, 11951-11958) in their most popular conformations. The spans (Omega = sigma(33) - sigma(11)) of all the tensors reported here are large ( approximately 34 ppm) and there are only very minor differences between helical and sheet residues. This is in contrast to the previous report in which Val, Ile and Thr were reported to have large ( approximately 12 ppm) differences in Omega between helical and sheet geometries. Apparently, only the beta-branched (beta-disubstituted) amino acids have such large CSA span (Omega) differences; however, there are uniformly large differences in the solution-NMR-determined CSA (Deltasigma = sigma(orth) - sigma(par)) between helices and sheets in all amino acids considered. This effect is overwhelmingly due to a change in shielding tensor orientation. With the aid of such shielding tensor orientation information, we computed Deltasigma values for all of the amino acids in calmodulin/M13 and ubiquitin. For ubiquitin, we find only a 2.7 ppm rmsd between theory and experiment for Deltasigma over an approximately 45 ppm range, a 0.96 slope, and an R(2) = 0.94 value when using an average solution NMR structure. We also report C(beta) shielding tensor results for these same amino acids, which reflect the small isotropic chemical shift differences seen experimentally, together with similar C(beta) shielding tensor magnitudes and orientations. In addition, we describe the results of calculations of C(alpha), C(beta), C(gamma)1, C(gamma)2, and C(delta) shifts in the two isoleucine residues in bovine pancreatic trypsin inhibitor and the four isoleucines in a cytochrome c and demonstrate that the side chain chemical shifts are strongly influenced by chi(2) torsion angle effects. There is very good agreement between theory and experiment using either X-ray or average solution NMR structures. Overall, these results show that both C(alpha) backbone chemical shift anisotropy results as well as backbone and side chain (13)C isotropic shifts can now be predicted with good accuracy by using quantum chemical methods, which should facilitate solution structure determination/refinement using such shielding tensor surface information.     

Melting of pentaerythritol tetranitrate (PETN) nanoconfined in controlled pore glasses (CPG)

The melting temperature depression of pentaerythritol tetranitrate, nanoconfined in controlled pore glasses (CPG), was systematically studied by differential scanning calorimetry (DSC). The solid–liquid interfacial energy σ _sl was obtained from the Gibbs–Thomson equation fit to melting temperature vs. reciprocal pore diameter. The pore size distribution of the CPG pores was also estimated from the DSC data. Pore sizes obtained from the manufacturer by BET are compared with those determined from the DSC curves using either the curves directly or by assuming spherical shaped confining cavities. The thermal mass vales are in better agreement with the BET estimation.     

Memory effects in chiral nematic liquid crystals doped with functionalised single-walled carbon nanotubes

Octadecylamine-functionalised single-walled carbon nanotubes (SWCNTs) were dispersed into nematic liquid crystals (LCs) doped with chiral molecules. The collective orientation of nematic LC molecules in helical layers was manipulated by varying dopant concentration. Highly anisotropic nature of SWCNTs enhanced the anisotropy of the LC as confirmed by polarised fluorescence spectroscopy. The π–π interaction of SWCNTs present in the planar alignment layers and twisted nematic LC molecules affects the molecular relaxation process. An irreversible electro-optic memory in the material has been observed.     

Ring current effects in crystals. Evidence from 13C chemical shift tensors for intermolecular shielding in 4,7-di-t-butylacenaphthene versus 4,7-di-t-butylacenaphthylene

13C chemical shift tensor data from 2D FIREMAT spectra are reported for 4,7-di-t-butylacenaphthene and 4,7-di-t-butylacenaphthylene. In addition, calculations of the chemical shielding tensors were completed at the B3LYP/6-311G** level of theory. While the experimental tensor data on 4,7-di-t-butylacenaphthylene are in agreement with theory and with previous data on polycyclic aromatic hydrocarbons, the experimental and theoretical data on 4,7-di-t-butylacenaphthene lack agreement. Instead, larger than usual differences are observed between the experimental chemical shift components and the chemical shielding tensor components calculated on a single molecule of 4,7-di-t-butylacenaphthene, with a root mean square (rms) error of +/-7.0 ppm. The greatest deviation is concentrated in the component perpendicular to the aromatic plane, with the largest value being a 23 ppm difference between experiment and theory for the 13CH2 carbon delta11 component. These differences are attributed to an intermolecular chemical shift that arises from the graphitelike, stacked arrangement of molecules found in the crystal structure of 4,7-di-t-butylacenaphthene. This conclusion is supported by a calculation on a trimer of molecules, which improves the agreement between experiment and theory for this component by 14 ppm and reduces the overall rms error between experiment and theory to 4.0 ppm. This intermolecular effect may be modeled with the use of nuclei independent chemical shieldings (NICS) calculations and is also observed in the isotropic 1H chemical shift of the CH2 protons as a 4.2 ppm difference between the solution value and the solid-state chemical shift measured via a 13C-1H heteronuclear correlation experiment.     

Determination of solvatochromic solvent polarity parameters for the characterisation of some nematic liquid crystal in anisotropic and isotropic phases

Characterisation of liquid crystals (LCs) as solvents is needed, to obtain the polarity and solvatochromic polarity parameters of these media. Polarity parameters demonstrate the effects of LC media on the photo-physical behaviour of solute molecules in an anisotropic medium. The practical limitations in determining solvent polarity scale parameters for LCs can overcome the overlapping absorption band of LCs and solvent-sensitive standard compounds or their insolubility in LCs. In this work, we report Kamlet–Abboud–Taft polarity functions of some nematic LCs in different temperatures and phases, isotropic and anisotropic, with the solvatochromic method, using the Reichardt's dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)-phenolate standard probe. In addition, a new azo and coumarin dye were used as probes to obtain some solvatochromic polarity parameters. Finally, a new polarity parameter, the LC anisotropic matrix, is introduced.     

Glycyl C(alpha) chemical shielding in tripeptides: measurement by solid-state NMR and correlation with X-ray structure and theory

We report here (13)C(alpha) chemical shielding parameters for central Gly residues in tripeptides adopting alpha-helix, beta-strand, polyglycine II, and fully extended 2 degrees structures. To assess experimental uncertainties in the shielding parameters and the effects of (14)N-(13)C(alpha) or (15)N-(13)C(alpha) dipolar coupling, stationary and magic angle spinning (MAS) spectra with and without (15)N decoupling were obtained from natural abundance and double-labeled samples containing [2-(13)C, (15)N]Gly. We find that accurate (<1 ppm uncertainty) shielding parameters are measured with good sensitivity and resolution in (15)N decoupled 1D or 2D MAS spectra of double-labeled samples. Compared to variations of isotropic shifts with peptide angles, those of (13)C(alpha) shielding anisotropy and asymmetry are greater. Trends relating shielding parameters to the 2 degrees structure are apparent, and the correlation of the experimental values with unscaled ab initio shielding calculations has an rms error of 3 ppm. Using the experimental data and the ab initio shielding values, the empirical trends relating the 2 degrees structure to shielding are extended to the larger range of torsion angles found in proteins.     

A method for the estimation of pore anisotropy in porous solids

In this work a method for the estimation of pore anisotropy, b, in porous solids is suggested. The methodology is based on the pore size distribution and the surface area distribution, both calculated from trivial N2 adsorption-desorption isotherms. The materials used for testing the method were six MCM-Alx solids in which the ordered pore structure (for x = 0) was gradually destroyed by the introduction of Al atoms (x = 5, 10, 15, 20, 50) into the solids. Additionally, four silicas having random porosity were examined, in which the surface of the parent material SiO2 (pure silica) was gradually functionalized with organosilicate groups of various lengths (triple bond Si-H, triple bond Si-CH2OH, triple bond Si-(CH2)3OH) in order to block a variable amount of pores. As pore anisotropy, the ratio bi = Li/Di is defined where Li and Di are the length and the diameter of each group of pores i filled at a particular partial pressure (Pi/P0). The ratio of the surface area Si over the pore volume Vi, at each particular pressure (Pi/P0), is then expressed as Si3/Vi2 = 16 pi Nibi = 16 pi lambdai, where Nibi is the number of pores having anisotropy bi which are filled at each pressure (Pi/P0) and lambdai is the total anisotropy of all the pores Ni belonging to the group i of pores. Then plot of lambdai vs (Pi/P0) provides a clear picture of the variation of the total pore anisotropy lambdai as the partial pressure (Pi/P0) increases. For the functionalized silicas there appears a continuous drop of lambdai as partial pressure (Pi/P0) increases, a fact indicating that both Ni) and bi are continuously diminished. In contrast, for the MCM-Alx materials a sudden kink of lambdai appears at the partial pressure where the well-defined mesopores are filled up, a fact indicating that at this point Ni and/or bi is large. The kink disappears as the ordered porosity is destroyed by increasing the x doping in MCM-Alx. The pore anisotropy bi of each group i of pores is then estimated using the expression (Si3/Vi2) = 8 pi NiriSi and plotting log(lambdai) vs log ri. From those plots, the values of si can be found and therefore the values of bi = 0.5riSi are next defined. In the MCM-Alx materials the maximum pore anisotropy b is very high (bi approximately 250) for x = 0. Then as mesoporosity is destroyed by increasing x, the maximum b values drop gradually to b approximately 11 (x = 5), b approximately 8 (x = 10), and b approximately 3 (x = 15). For x = 20 and x = 50, the maximum b obtains values equal to unity. The same phenomena, although less profound, are also observed for the functionalized silicas, where the anisotropy b is altered by the process of functionalization and from bi approximately 0.5 for the nonfunctionalized or bi approximately 0.9 for the solid functionalized with Si-H groups drops to b = 0.3 and b = 0.2 for the solid functionalized with triple bond Si-(CH2)OH and triple bond Si-(CH2)3OH, respectively. A correlation factor F is suggested in cases where the pore model departs from the cylindrical geometry.