Structure and ultrafast dynamics of liquid water: a quantum mechanics/molecular mechanics molecular dynamics simulations study

A quantum mechanics/molecular mechanics molecular dynamics simulation was performed for liquid water to investigate structural and dynamical properties of this peculiar liquid. The most important region containing a central reference molecule and all nearest surrounding molecules (first coordination shell) was treated by Hartree-Fock (HF), post-Hartree-Fock [second-order Moller-Plesset perturbation theory (MP2)], and hybrid density functional B3LYP [Becke's three parameter functional (B3) with the correlation functional of Lee, Yang, and Parr (LYP)] methods. In addition, another HF-level simulation (2HF) included the full second coordination shell. Site to site interactions between oxygen-oxygen, oxygen-hydrogen, and hydrogen-hydrogen atoms of all ab initio methods were compared to experimental data. The absence of a second peak and the appearance of a shoulder instead in the gO-O graph obtained from the 2HF simulation is notable, as this feature has been observed so far only for pressurized or heated water. Dynamical data show that the 2HF procedure compensates some of the deficiency of the HF one-shell simulation, reducing the difference between correlated (MP2) and HF results. B3LYP apparently leads to too rigid structures and thus to an artificial slow down of the dynamics.     

Extreme swelling of a lyotropic lamellar liquid crystal

The evolution of the OBS/water/decane/pentanol lyotropic lamellar crystal is followed from 0% to more than 90% decane content. The lamellar spacing (d) varies then from 35 Å to 11000 Å. The swelling is followed with small angle x-ray scattering and the Bragg divergence in the intensity is found to disappear in moderately swollen lamellar crystal (d from 200 Å up to 800 Å) while the central scattering increases. More striking is the reappearance of the Bragg divergences observed by SAXS (d from 800 Å to 1100 Å) and for extremely swollen lamellar crystals in the angular distribution of scattered light (d from 2 000 Å to 10 000 Å). We discuss these observations along the lines of the recent models of swollen lamellar liquid crystals and in particular the apparent evolution of the dilute lamellae.     

Spontaneous three-dimensional nanostructure formation of perfluoroalkyl terminated liquid crystal: a molecular dynamics simulation study

Structure formation of a perfluoroalkyl terminated liquid crystal molecule was studied by molecular dynamics simulations. Two distinct structures with smectic-C-like layers and with bundles (blocks) of collapsed layers were spontaneously formed depending on the simulation temperatures. The bundles in the latter structure were somewhat positionally ordered (with respect to the small angle spots in its structure function) and orientationally isotropic overall even though the molecules making each bundle were well oriented. These characteristics of the simulated system well correspond to the cubic phase of the real system, and an even more precisely correspond to the proposed cubic structure model with respect to its hierarchical structure.     

Structure conversions of cellulose IIII crystal models in solution state: a molecular dynamics study

This paper re-examines our previous molecular dynamics (MD) study on cellulose III_I crystal models with finite dimensions solvated in explicit water molecules. Eight crystal models, differing in a constituent lattice plane and dimensions, were studied. One calculation allowed for O–H and C–H bond stretching, and had a small time step of 0.5 fs. The other calculation adopted non-scaling factors of the 1–4 non-bonded interactions. As in our previous study, in the former MD calculations, six of the eight crystal models exhibited structure conversion with cooperative chain slippages generated by a progressive fiber bend. This converted the initial non-staggered chain packing of cellulose III_I into a near one-quarter staggering and gave the crystal model a triclinic-like configuration. In contrast, in the non-1–4 scaling MD calculations, all of the eight crystal models retained the initial cellulose III_I crystal structure. Another series of non-1–4 scaling MD calculations were performed for the four crystal models containing chains with a degree of polymerization (DP) of 40 at 370 K, which simulated hot water treatment to convert cellulose III_I to Iβ. Some of the hydroxymethyl groups irreversibly rotated from gt into tg conformation. This accompanied exchange of the intrasheet hydrogen bonding scheme along the (1 ?1 0) lattice plane from O2–O6 to O3–O6. The original corrugated (1 ?1 0) chain sheet was partly converted into a cellulose I-like flat chain sheet.     

Phase behavior of lyotropic rigid-chain polymer liquid crystal studied by dissipative particle dynamics

The phase behavior of lyotropic rigid-chain liquid crystal polymer was studied by dissipative particle dynamics (DPD) with variations of the solution concentration and temperature. A chain of fused DPD particles was used to represent each mesogenic polymer backbone surrounded with the strongly interacted solvent molecules. The free solvent molecules were modeled as independent DPD particles, where each particle includes a lump of solvent molecules with the volume roughly equal to the solvated polymer segment. The simulation shows that smectic-B (S(B)), smectic-A (S(A)), nematic (N), and isotropic (I) phases exist within certain regions in the temperature and concentration parameter space. The temperature-dependent S(B)∕S(A), S(A)∕N, and N∕I phase transitions occur in the high concentration range. In the intermediate concentration range, the simulation shows coexistence of the anisotropic phases and isotropic phase, where the anisotropic phases can be the S(B), S(A), or N phases. Mole fraction and compositions of the coexisted phases are determined from the simulation, which indicates that concentration of rigid rods in isotropic phase increases as the temperature increases. By fitting the orientational distribution function of the systems, the biphasic coexistence is further confirmed. From the parameter α obtained for the simulation, the distribution of the rigid rods in the two coexistence phases is quantitatively evaluated. By using model and simulation methods developed in this work, the phase diagrams of the lyotropic rigid-chain polymer liquid crystal are obtained. Incorporating the solvent particles in the DPD simulation is critical to predict the phase coexistence and obtain the phase diagrams.     

Molecular location in a nonaqueous lyotropic liquid crystal polymer

A surfactant bis[2-(10-undecenoyloxycarbonyl)ethyl] (p-vinylbenzoyl) methylammonium chloride formed a lamellar liquid crystal in native form and retained the structure after polymerization. Addition of heptadiene, of glycerylmonomethacrylate, and of both to the surfactant monomer gave an isotropic solution, which was transformed to a lamellar liquid crystal after polymerization. Low angle X-ray diffractometry was used to determine the interlayer spacing and to estimate the location of the added molecules. 1.6-Heptadiene was located between methyl group layers of the surfactant chains with 46 vol % of the molecules penetrating between the hydrocarbon chains of the surfactant. Addition of both the polar and the nonpolar monomer followed by polymerization caused the latter to be expelled from the space in between the chains.     

Nematic-isotropic interfacial tension anisotropy of a calamitic lyotropic liquid crystal

In a planar oriented sample of a calamitic nematic lyotropic system (mixture of sodium lauryl sulphate/water/decanol), isotropic pretransitional domains appear at the nematic to isotropic transition. The domains are oblong in shape with the long axis along the orientational direction. We show experimental evidence that this oblong shape is determined by the nematic-isotropic interfacial tension anisotropy. Two uniparametric models of simple angular dependences for the interfacial tension are tested. Using the differential system obtained from the Young-Laplace condition at the nematic-isotropic interface, the domain shape can be numerically calculated for each value of the interfacial tension anisotropy. By processing the values of the transmitted light through both an isolated isotropic domain and its surrounding nematic zone, we obtain the anisotropy of the interfacial tension as the main fitting parameter. An estimation of the ratio of the extreme values for the interfacial tension is given.     

Spatial heterogeneity in a lyotropic liquid crystal with hexagonal phase

Non-ionic surfactant hexaethylene glycol, C(12)E(6), in water self-assembles into various kinds of mesophases by varying the surfactant concentration. A spatial heterogeneity was discussed on the basis of the diffusion of probe particles dispersed in the C(12)E(6)-water solution. Interestingly, at 50 wt% C(12)E(6) where the hexagonal structure was formed, two kinds of motion of probe particles were observed: some particles normally diffused while others were restricted, indicating the existence of a heterogeneity in the physical properties. Such heterogeneity can be explained in terms of heterogeneous structures composed of hexagonal domains with isotropic-like regions.     

乙基氰乙基纤维素溶致性液晶的研究

纤维素和纤维素衍生物在适当的溶剂中可以形成溶致性液晶, 乙基氰乙基纤维素是纤维素的一种混合醚类衍生物, 本文研究了其溶致性液晶的形成, 结构以及不同溶剂对形成液晶所产生的影响.     

三组份非水体系的溶致液晶的研究

在非水三元体系(卵磷脂,乙二醇,甲醇)中能得到溶致液晶,其中溶剂必须经过严格的脱水处理,本文使用偏振光显微镜确定溶致液晶的相图,获得一些典型照片,用低角度X射线衍射仪测定其几何参数,结果表明所得液晶为层状液晶,并对在该体系中,由于甲醇浓度的改变而引起了卵磷脂分子的平均截面积、液晶层间距和其渗透率变化规律作了理论探讨和分析。     

Structure and diffusion of nanoparticle monolayers floating at liquid/vapor interfaces: a molecular dynamics study

Large-scale molecular dynamics simulations are used to simulate a layer of nanoparticles floating on the surface of a liquid. Both a low viscosity liquid, represented by Lennard-Jones monomers, and a high viscosity liquid, represented by linear homopolymers, are studied. The organization and diffusion of the nanoparticles are analyzed as the nanoparticle density and the contact angle between the nanoparticles and liquid are varied. When the interaction between the nanoparticles and liquid is reduced the contact angle increases and the nanoparticles ride higher on the liquid surface, which enables them to diffuse faster. In this case the short-range order is also reduced as seen in the pair correlation function. For the polymeric liquids, the out-of-layer fluctuation is suppressed and the short-range order is slightly enhanced. However, the diffusion becomes much slower and the mean square displacement even shows sub-linear time dependence at large times. The relation between diffusion coefficient and viscosity is found to deviate from that in bulk diffusion. Results are compared to simulations of the identical nanoparticles in 2-dimensions.     

Deuteron relaxation study of D2O motions in a lyotropic liquid crystal

The water molecules adsorbed at the soap—water interface in the mesophases of potassium laurate—D₂O system reorient rapidly while diffusing along the interface; our results also suggest that the dynamical behaviour of the aqueous and paraffinic media are strongly correlated.     

Shear rheology of lyotropic liquid crystals: a case study

We have investigated the rheological properties of lyotropic liquid crystals (LCs) formed by self-assembled neutral lipids and water, their relationship with the topology of the structure, and their dependence on temperature and water content. The phase diagram of a representative monoglyceride-water system, determined by combining cross-polarized optical microscopy and small-angle X-ray scattering (SAXS), included four structures: lamellar, hexagonal, gyroid bicontinuous cubic (Ia3d), and double diamond bicontinuous cubic (Pn3m), as well as several regions of two-phase coexistence of some of the above structures. Rheology in the linear viscoelastic regime revealed a specific signature that was characteristic of the topology of each structure considered. The order-order transitions lamellar-to-cubic and cubic-to-hexagonal, as well as the order-disorder transitions from each LC to an isotropic fluid, were easily identified by following the development of the storage and loss moduli, G' and G', respectively. The viscoelastic properties of both bicontinuous cubic phases were shown to be strongly frequency-dependent, following a pseudo-Maxwell behavior, with multiple relaxation times. Cubic-to-cubic transitions were nicely captured by scaling the longest relaxation time, tau, with either temperature or water volume fraction. Therefore, the set of the three main parameters used to establish the rheological behavior of the structure, that is, G', G', and relaxation time, tau, constitutes a consistent ensemble to identify the structures of the liquid crystal. Finally, relaxation spectra, extracted for all liquid crystalline phases, allowed an additional possible identification criterion of the various structures considered.     

The alignment of dichroic dyes in a nematic liquid crystal: a molecular dynamics investigation

The absorption properties of a dye molecule depend on its orientation relative to the light source. Thus the ability to predict how well a particular dye aligns with a liquid crystal host will improve the design of smart materials. One measurement of this alignment is the order parameter, which can be calculated from molecular dynamics simulations. The results for three dyes are presented here. The orientation of the long molecular axis of the dye relative to the liquid crystal director can range from perpendicular to parallel, with the dyes studied having an average order parameter of the dye similar to the average order parameter of the host.     

Self-screening of Langmuir-Blodgett films by a discotic micellar lyotropic liquid crystal

The influence of the surface treatment on the anisotropic part of the surface tension of a lyotropic discotic micellar nematic liquid crystal doped with ferrofluid is analysed. The treatment involves Langmuir-Blodgett (LB) films deposited on the glass substrates. Textural observations and phase-shift measurements of the transmitted light were carried out. A phenomenological model which allows calculation of the director average orientation in the bulk and at the surfaces is used for interpreting the experimental data. Our results show that the average director alignment depends on the concentration of the magnetic grains of ferrofluid at the glass surfaces. On the contrary, it is practically independent of the nature of the molecule deposited on the glass substrate. According to the model, the flat glass surface, independently of the treatment or the absence of any treatment, stabilizes onto itself a lamellar layer (or bilayer) formed by the amphiphilic molecules of the liquid crystal. This layer screens the effect of the LB film (or of the pure untreated substrate) on the alignment of the lyotropic nematic mesophase.     

Radical polymerization behavior and molecular weight development of homologous monoacrylate monomers in lyotropic liquid crystal phases

Polymerization in highly ordered lyotropic liquid‐crystalline (LLC) media enables controllable synthesis of polymers possessing interesting nanostructure and physical properties. This study investigates the radical polymerization rate and molecular weight (MW) development of monoacrylates of different aliphatic tail length in a range of LLC phases. Polymerization rate data were acquired using photodifferential scanning calorimetry, and linear polymer MW was determined with gel permeation chromatography. Polymerization occurs much more rapidly, and higher MW is attained in the ordered LLC phases relative to isotropic solutions and neat polymerization. These properties change significantly as a function of LLC phase and monomer structure. A direct relationship is observed between polymer MW formation and the polymerization rate. Definitive changes in rate and MW were observed at phase boundaries, indicating the important role of solvent order. This study demonstrates how solvent ordering effects can be used to control polymer MW and rate of polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 144–154     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20-36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.     

Proton NMR relaxation study of molecular dynamics of chromonic liquid crystal Edicol Sunset Yellow

Proton nuclear magnetic resonance (¹H NMR) relaxometry, over about five decades in Larmor frequency, and pulsed field gradient NMR were used to study the molecular dynamics in the chromonic nematic and isotropic phases of stacked molecules of the binary mixture composed by Edicol Sunset Yellow (ESY) and deuterated water. Our results evidence that in both phases collective motions are responsible for the spin-lattice relaxation dispersion in the Larmor frequency range below 1 MHz. In the nematic phase, the collective motion are attributed to columnar undulations within the stacked molecules, while, in the isotropic phase, the results are explained by local order fluctuations due to the formation of the stacks. The high frequency dispersion was explained by individual molecular motions like rotations around and perpendicular to the stack axis, and also self-diffusion.     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20–36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.