Isotropic Liquid Research Articles

Second harmonic Rayleigh scattering optical activity of single Ag nanohelices in a liquid.

Determining the chirality of molecules and nanoparticles often relies on circular dichroism and optical rotation: two chiral optical (chiroptical) effects in the linear optical regime. Although these linear effects are weak compared to nonlinear chiroptical effects, they have the advantage of being measured in isotropic liquids - free from the complications of anisotropy. Recently, a nonlinear effect: hyper-Rayleigh scattering optical activity (HRS OA) has been shown to reliably distinguish between the two chiral forms of Ag nanohelices, suspended in isotropic liquids. However, this first demonstration of HRS OA also opened new questions. For instance, at a fundamental level, it is not clear what the role of interactions between nanoparticles is. Moreover, the influence of the ultrafast pulse chirp is unknown. Here, we demonstrate HRS OA from well below two Ag nanohelices in the illumination volume, precluding any interactions. Additionally, we performed the first measurements of HRS depolarization ratios in this system and find a value of ≈1. We also show that HRS is highly robust against the chirp of the ultrafast pulses. An important reason for the strong (down to single nanohelix) sensitivity of our experiments is the large chiroptical interaction at the fundamental frequency; this point is illustrated with two sets of numerical simulations of the electromagnetic near-fields. Our results highlight HRS OA as a highly sensitive experimental method for characterization of chiral solutions/suspensions, in tiny illumination volumes.

Shear-induced birefringence in an optically isotropic cubic liquid crystalline phase.

We report an unusually strong flow-induced birefringence in an optically isotropic cubic phase occurring below the isotropic chiral conglomerate phase formed by a low-molecular-weight polycatenar mesogen. The transition into the birefringent state occurs thresholdless and the induced birefringence is comparable with that observed in polymeric systems. We suggest that the flow-induced deformation of the cubic structure is responsible for the strong rheo-optical response.

Probing a microviscosity change at the nematic-isotropic liquid crystal phase transition by a ratiometric flapping fluorophore.

Understanding the microviscosity of soft condensed matter is important to clarify the mechanisms of chemical, physical or biological events occurring at the nanoscale. Here, we report that flapping fluorophores (FLAP) can serve as microviscosity probes capable of detecting small changes. By the ratiometric fluorescence analysis, one of the FLAP probes detects a macroscopic viscosity change of a few cP, occurring at the thermal phase transition of a nematic liquid crystal. We discuss the impact of the chemical structure on the detection capability, and the orientation of the FLAP molecules in the ground and excited states. This work contributes to experimentally providing a molecular picture of liquid crystals, which are often viewed as a continuum.

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety.

The cold crystallization mechanism of 1-{[4′-(4″-nitrophenylazo)phenyloxy]}hexyl-3-methyl-1H-imidazol-3-ium tetrafluoroborate ionic liquid crystal was investigated based on thermal analysis, structural analysis, infrared spectroscopy, and quantum chemical calculations. By conducting thorough structural characterization, we found that the prerequisite for cold crystallization is the irreversible molecular conformational alteration induced by the initial heating of the as-grown crystal into a smectic liquid crystal. The originally linear cation molecule bends and forms a step-stair conformation that persists throughout the subsequent heating and cooling processes as phase transition occurs from the crystal phase to the liquid crystal phase and then to the isotropic liquid phase. The formation of cold crystal occurs because of the choice of molecular stability over crystalline stability. Given the exothermic anomaly exhibited upon heating generic crystals to cold crystals, these findings demonstrate the promising potential of this ionic liquid crystal for thermal energy storage applications.

Photochromic spiropyran-based liquid crystals

We present a new type of light responsive self-assembling structures based on a spiropyran photoswitchable unit. The spiropyran central part was modified by functional groups, which enabled the connection of two structurally different elongating parts. Two series of compounds were prepared with reversed orientation of the ester as a linkage group in the molecular core. The properties of the target materials were studied by differential scanning calorimetry and polarized light optical microscopy, which confirmed the presence of a nematic phase for most of the materials. In case of a trifluromethyl-substituted compound, a sequence of nematic – smectic A – smectic C phase was detected and confirmed by X-ray diffraction analysis. The photochromic properties of compounds were studied in solution as well as in mesophases. In the condensed state, UV light-induced switching from the spiropyran form to the merocyanine dye led to isothermal transition from the liquid crystalline phase to the isotropic liquid.

Synthesis, characterisation, and effects of molecular structure on phase behaviour of 4-chloro-1,3-diazobenzene bent-core liquid crystals with high photosensitivity

ABSTRACT A series of new compounds were synthesised by adding azo functional groups and chlorine substituent to the central bent-cores to form a 4-chloro-1,3-dizaophenylene bent-core. The structure, mesogenic properties, and photosensitivity of these compounds were characterised. The results show these synthesised compounds exhibit a broad temperature window up to 63.8°C for nematic phase and the rapid rate of trans – cis photoisomerisation. For instance, at 95°C, compound 4c in nematic phase became an isotropic liquid under UV-irradiation in 3 s and could be restored to nematic under natural visible light in 5 s. Quantum mechanics calculation confirms that using azos instead of esters as the central linkages can effectively reduce the molecular dipole moment, which appears to promote favourable mesogenic and photonic characteristics. Moreover, varying the carbon number in the terminal alkyl chains can alter molecular dipole moment and polarisability anisotropy, which are strongly correlated with the phase transition temperature and temperature range of the nematic phase. These findings suggest that 1) changing azo group position can effectively alter the intermolecular interactions by varying molecular polarity and polarisability; 2) reducing long-range electrostatic interactions can promote favourable mesogenic and possibly photonic properties of azobenzene bent-core liquid crystal.

How Far Can We Push the Rigid Oligomers/Polymers toward Ferroelectric Nematic Liquid Crystals?

The emerging ferroelectric nematic (NF) liquid crystal is a novel 3D-ordered liquid exhibiting macroscopic electric polarization. The combination of the ultrahigh dielectric constant, strong nonlinear optical signal, and high sensitivity to the electric field makes NF materials promising for the development of advanced liquid crystal electroopic devices. Previously, all studies focused on the rod-shaped small molecules with limited length (l) range and dipole moment (μ) values. Here, through the precision synthesis, we extend the aromatic rod-shaped mesogen to oligomer/polymer (repeat unit up to 12 with monodisperse molecular-weight dispersion) and increase the μ value over 30 Debye (D). The NF phase has a widespread existence far beyond our expectation and could be observed in all the oligomer/polymer length range. Notably, the NF phase experiences a nontrivial evolution pathway with the traditional apolar nematic phase completely suppressed, i.e., the NF phase nucleates directly from the isotropic liquid phase. The discovery of thte ferroelectric packing of oligomer/polymer rods not only offers the concept of extending the NF state to oligomers/polymers but also provides some previously overlooked insights in oxybenzoate-based liquid crystal polymer materials.

Photosensitive Bent-Core Liquid Crystals with Laterally Substituted Azobenzene Unit

Photosensitive liquid crystals represent an important class of functional materials that experience rapid development. Hereby, we present novel bent-core liquid crystals bearing a lateral substitution on the central core and in the vicinity of the photosensitive unit—an azo group. The azo group enables fast (E)-to-(Z)-isomerization upon irradiation with UV-light and visible light, while the substitution facilitates the high stability of the photochemically formed (Z)-isomer. The effectiveness of the irradiation and the composition of photostationary states was determined by UV/Vis and 1H NMR spectroscopy. A nematic phase formed by the materials was characterized by differential scanning calorimetry and optical polarizing microscopy. We show that the materials easily change their relative configuration of the N=N double bond not only in solution, but also in the mesophase, which leads to fast isothermal phase transition from the nematic phase to isotropic liquid.

Time-Variable Chiroptical Vibrational Sum-Frequency Generation Spectroscopy of Chiral Chemical Solution.

Vibrational sum-frequency generation (VSFG) spectroscopy, a surface-specific technique, was shown to be useful even for characterizing the vibrational optical activity of chiral molecules in isotropic bulk liquids. However, accurately determining the spectroscopic parameters is still challenging because of the spectral congestion of chiroptical VSFG peaks with different amplitudes and phases. Here, we show that a time-variable infrared-visible chiroptical three-wave-mixing technique can be used to determine the spectroscopic parameters of second-order vibrational response signals from chiral chemical liquids. For varying the delay time between infrared and temporally asymmetric visible laser pulses, we measure the chiral VSFG, achiral VSFG, and their interference spectra of bulk R-(+)-limonene liquid and perform a global fitting analysis for those time-variable spectra to determine their spectroscopic parameters accurately. We anticipate that this time-variable VSFG approach will be useful for developing nearly background-free chiroptical characterization techniques with enhanced spectral resolution.

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety.

With a view to fabricating a new remote input-output system by applying functional ionic liquid crystalline (ILC) materials, we have developed novel ILC compounds containing a nitroxide radical unit in the organic cations, which show an enantiotropic smectic A (SmA) phase. We have implemented the magnetic manipulation of a droplet of one of the ILC compounds on the basis of the intermolecular magnetic interactions between radical moieties. This ILC monoradical compound shows a 55 % larger increase in paramagnetic susceptibility at the solid-to-LC melting point in the first heating process than the non-ionic LC monoradical compounds. It is most likely owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. The increased molar magnetic susceptibility is preserved not only in the SmA phase but also in the isotropic liquid and solid phases during the first cooling process.

Liquid Crystals Investigation Behavior on Azo-Based Compounds: A Review.

Liquid crystal is an intermediate phase between the crystalline solid and an isotropic liquid, a very common substance in our daily lives. Two major classes of liquid crystal are lyotropic, where a liquid crystal is dissolved in a specific solvent under a particular concentration and thermotropic, which can be observed under temperature difference. This review aims to understand how a structure of a certain azo compound might influence the liquid crystal properties. A few factors influence the formation of different liquid crystals: the length of the alkyl terminal chain, inter/intra-molecular interaction, presence of spacer, spacer length, polarization effects, odd-even effects, and the presence of an electron-withdrawing group or an electron-donating group. As final observations, we show the compound’s different factors, the other liquid crystal is exhibited, and the structure–property relationship is explained. Liquid crystal technology is an ideal system to be applied to products to maximize their use, especially in the electronic and medical areas.

Mirror Symmetry Breaking and Network Formation in Achiral Polycatenars with Thioether Tail.

Mirror symmetry breaking in systems composed of achiral molecules is of importance for the design of functional materials for technological applications as well as for the understanding of the mechanisms of spontaneous emergence of chirality. Herein, we report the design and molecular self‐assembly of two series of rod‐like achiral polycatenar molecules derived from a π‐conjugated 5,5’‐diphenyl‐2,2’‐bithiophene core with a fork‐like triple alkoxylated end and a variable single alkylthio chain at the other end. In both series of liquid crystalline materials, differing in the chain length at the trialkoxylated end, helical self‐assembly of the π‐conjugated rods in networks occurs, leading to wide temperature ranges (>200 K) of bicontinuous cubic network phases, in some cases being stable even around ambient temperatures. The achiral bicontinuous cubic Ia 3‾ d phase (gyroid) is replaced upon alkylthio chain elongation by a spontaneous mirror symmetry broken bicontinuous cubic phase (I23) and a chiral isotropic liquid phase (Iso1 [*]). Further chain elongation results in removing the I23 phase and the re‐appearance of the Ia 3‾ d phase with different pitch lengths. In the second series an additional tetragonal phase separates the two cubic phase types.

Hydrodynamics of simple active liquids: the emergence of velocity correlations

We derive the hydrodynamics for a system of N active, spherical, underdamped particles, interacting through conservative forces. At the microscopic level, we represent the evolution of the particles in terms of the Kramers equation for the probability density distribution of their positions, velocities, and orientations, while at a mesoscopic level we switch to a coarse-grained description introducing an appropriate set of hydrodynamic fields given by the lower-order moments of the distribution. In addition to the usual density and polarization fields, the hydrodynamics developed in this paper takes into account the velocity and kinetic temperature fields, which are crucial to understanding new aspects of the behavior of active liquids. By imposing a suitable closure of the hydrodynamic moment equations and truncation of the Born–Bogolubov–Green–Kirkwood–Yvon hierarchy, we obtain a closed set of mesoscopic balance equations. At this stage, we focus our interest on the small deviations of the hydrodynamic fields from their averages and apply the methods of the theory of linear hydrodynamic fluctuations. Our treatment sheds light on the peculiar properties of isotropic active liquids and their emergent dynamical collective phenomena, such as the spontaneous alignment of the particle velocities. We predict the existence within the liquid phase of spatial equal-time Ornstein–Zernike-like velocity correlations both for the longitudinal and the transverse modes. At variance with active solids, in active liquids, the correlation length of the transverse velocity fluctuations is sensibly shorter than the length of the longitudinal fluctuations. In particular, the latter depends on the sound speed and increases with the persistence time, while the former displays a weaker dependence on these parameters. Finally, within the same framework, we derive the dynamical structure factors and the intermediate scattering functions and discuss how the velocity ordering persists in time. We find that the velocity decorrelates on a time-scale much longer than the one characteristic of passive fluids.

Investigation of the aggregation behaviour of the anionic surfactant sodium dodecyl sulfate in ionic liquids 1-allyl-3-methylimidazolium chloride and 1-Ethyl-3-methylimidazolium diethyl phosphate

We investigated the aggregation behaviour of the anionic surfactant sodium dodecyl sulfate (SDS) in 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid at three temperatures 323 K, 333 K and 343 K using 1H Nuclear Magnetic Resonance (NMR) chemical shift and Pulsed-Field Gradient (PFG) spin-echo NMR self-diffusion measurements. Chemical shifts of SDS protons and diffusion coefficients of SDS as a function of the surfactant concentration have breakpoints, which indicate an onset of the surfactant micellisation. We estimated the critical micelle concentration (cmc) with high accuracy from SDS methyl protons' chemical shifts and the micelles' average aggregation number from diffusion coefficients. The formation of micelles does not influence the diffusion and chemical shifts of AMIMCl.We determined water concentration in the samples from the NMR spectra. We did not find evidence that water affects the aggregation process since water content practically does not influence the SDS protons' chemical shifts and diffusion coefficients. However, water appears to influence the diffusion and chemical shifts of AMIMCl.We also investigated the behaviour of SDS in 1-Ethyl-3-methylimidazolium diethyl phosphate (EMIMDEP) hydrophilic ionic liquid. The value of the Gordon parameter of EMIMDEP indicates that it does not possess the ability to support the self-assembly of amphiphiles. Within this work, we treat the system SDS/EMIMDEP as a reference one.SDS forms a lamellar phase in AMIMCl at high concentration, as revealed by Small Angle X-ray Scattering (SAXS) and Polarised Optical Microscopy (POM) investigations. At about 358 K, a transition from the lamellar phase to the isotropic liquid phase occurs. No other liquid-crystalline phase in this system was determined.

Optical Activity in Third‐Harmonic Rayleigh Scattering: A New Route for Measuring Chirality

AbstractIn 3D isotropic liquids, optical third‐harmonic generation is forbidden, with circularly polarized light (CPL). Yet the associated nonlinear susceptibility directly influences the optical properties at the fundamental frequency by intensity dependence (Kerr effect). Here, the hidden third‐harmonic optical properties upon CPL illumination are revealed by demonstrating a new effect, in hyper‐Rayleigh scattering. This effect is succinctly enunciated: the intensity of light scattered at the third‐harmonic frequency of the CPL incident light depends on the chirality of the scatterers. It is referred to as third‐harmonic (hyper) Rayleigh scattering optical activity (THRS OA) and was observed from Ag nanohelices randomly dispersed in water. The first analytical theory model for the new effect in nanohelices is also provided, highlighting the role of localized transition dipoles along the helical length. THRS OA is remarkably user‐friendly. It offers access to intricate optical properties (hyperpolarizabilities) that have so far been more easily accessible by computation and that are essential for the understanding of light−matter interactions. The new effect could find applications in hyper‐sensitive characterization of the chirality in molecules and in nanostructures; this chirality plays a fundamental role in the function of bio/nano‐machinery, with promising applications in next generation technologies.

ПЕРЕТВОРЕННЯ ІМПУЛЬСНОЇ ЕНЕРГІЇ В МІКРОХВИЛІ В НЕЛІНІЙНИХ ЛІНІЯХ ПЕРЕДАЧІ

Purpose: Experimental results and numerical simulations are presented, concerning effects of microwave generation in coaxial transmission lines which are fed with unipolar, high voltage electric pulses. The work is aimed at clarifying the relative importance of several mechanisms that could be responsible for the appearance of microwave-frequency oscillations in the course of pulse propagation through the guiding structure. Design/methodology/approach: Dispersive and filtering properties of coaxial waveguides that involve three structural sections are discussed. These latter follow one another along the axis of symmetry. Two identical sections at the input and output are filled with an isotropic liquid dielectric, while the middle part may, in addition, be either partially or fully filled with a non-conductive gyrotropic material. The inserted core represents a set of ferrite rings showing a nonlinear response to the initial high voltage, pulsed excitation. Throughout the series of measurements, the diameters of the inner conductor and of the ferrite core were kept constant. The outer conductor’s diameter was varied to permit analysis of the effect of that size proper and of the degree to which the cross-section is fi lled with ferrite. The gyrotropic properties of the ferrimagnetic material were realized through application of a magnetic bias field from an external coil. The measurements were made for a variety of pulsed voltage magnitudes from the range of hundreds of kilovolts, and magnetic bias fields of tens kiloamperes per meter. Findings: As observed in our experiments, as well as in papers by other writers, a unipolar pulse coming from the radially uniform front-end section, further on gives rise to quasi-monochromatic voltage oscillations. These appear as soon as the pulse has advanced a sufficient distance into the radially nonuniform portion of the guide. The oscillations may consist of a small number of quasi-periods, which suggests a large spectral line width. However, by properly selecting geometric parameters of the wave guiding line and the characteristics of the initial pulsed waveform it proves possible to obtain output frequencies of about units of gigahertz and pulse powers at subgigawatt levels. Conclusions: The frequencies and amplitudes of the appearing oscillations, as well as their spectral widths, are governed by the complex of dispersive and non-linear properties of the guiding structure. The diameters of the inner and outer coaxial conductors in the line, diameter of the ferrimagnetic insert and its intrinsic linear dispersion determine the set of waveguide modes capable of propagating through the line. An oscillating part of the waveform may appear and get separated from the main body of the pulse if it has originated at a higher frequency than the cut-off value for a different mode than the initial TEM. Key words: unipolar pulse, coaxial transmission line, microwave frequency oscillations, dispersion laws, waveguide modes

Polymer stabilized isotropic phase liquid crystals with large Kerr constant

ABSTRACT In this paper, we reported a polymer stabilised isotropic phase liquid crystal (PSILC). The influences of different content of chiral dopant and polymer monomer on PSILC were studied. Adding the proper proportion and total content of polymer monomer TMPTA and C12A into liquid crystal with 1.0 wt.% chiral dopant R5011, and UV photo-polymerisation at the isotropic phase, we obtain the Kerr constant greater than 10 nm/V2, hysteresis less than 2.0% and fast response in PSILC.

Synthesis and Characterization of Bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) (X = H, p-CH3O, p-Br) with Symmetry- and Distance-Dependent Vibrational Circular Dichroism Enhancement and Sign Inversion.

The enantiopure Schiff bases (R or S)-N-1-(X-C6H4)ethyl-2-hydroxy-1-naphthaldimine {X = H [(R or S)-HL1], p-CH3O [(R or S)-HL2], and p-Br [(R- or S)-HL3]} react with cobalt(II) acetate to give bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) {X = H [Λ/Δ-Co-(R or S)-L1], p-CH3O [Λ/Δ-Co-(R or S)-L2], and p-Br [Λ/Δ-Co-(R or S)-L3]} (1–3), respectively. Induced Λ and Δ chirality originates at the metal center of the C2-symmetric molecule in pseudotetrahedral geometry. Differential scanning calorimetry analyses explored the thermal stability of the complexes, which undergo reversible phase transformation from crystalline solid to isotropic liquid phase for 1 and 3 but irreversible phase transformation for 2. Like other cobalt(II) complexes, compounds 1–3 exhibit a continuous ensemble of absorption and circular dichroism bands, which span from the UV to IR region and can be collected into a superspectrum. Infrared vibrational circular dichroism (IR-VCD) spectra witness the coupling between Co2+-centered low-lying electronic states and ligand-centered vibrations. The coupling produces enhanced and almost monosignate VCD spectra, with both effects being mode-dependent in terms of the A or B symmetry (in the C2 point group) and distance from the Co2+ core.

Shear-Coated Linear Birefringent and Chiral Cellulose Nanocrystal Films Prepared from Non-Sonicated Suspensions with Different Storage Time.

Nanocelluloses are very attractive materials for creating structured films with unique optical properties using different preparation techniques. Evaporation-induced self-assembly of cellulose nanocrystals (CNC) aqueous suspensions produces iridescent films with selective circular Bragg reflection. Blade coating of sonicated CNC suspensions leads to birefringent CNC films. In this work, fabrication of both birefringent and chiral films from non-sonicated CNC suspensions using a shear-coating method is studied. Polarization optical microscopy and steady-state viscosity profiles show that non-sonicated CNC suspensions (concentration of 6.5 wt%) evolve with storage time from a gel-like shear-thinning fluid to a mixture of isotropic and chiral nematic liquid crystalline phases. Shear-coated films prepared from non-sonicated fresh CNC suspensions are birefringent, whereas films prepared from suspensions stored several weeks show reflection of left-handed polarized light. Quantification of linear and circular birefringence as well circular dichroism in the films is achieved by using a Mueller matrix formalism.

Investigation of phase transitions in liquid crystal 12BBAA using window clustering of infrared spectra

The k-means cluster analysis has been applied to the temperature-dependent infrared spectra of 4-bromobenzylidene-4′-dodecyloxyaniline (12BBAA). This method appears to be particularly sensitive to the tracking of the melting process of alkyl chains. 12BBAA may form a variety of phases including: isotropic liquid, smectic A, crystalline smectic B and crystal phase. Clustering methods are helpful tool for detection of phase transitions, but do not provide information on the structural changes due to the phase transitions. For this reason, window clustering analysis method has been proposed. Multivariate data has been divided into small spectral windows, and then cluster analysis has been applied for each data window. This approach allows to reduce the dimensionality of large data set, while reveals the spectral characteristic of given phase associated with various regions of spectra.