This work was supported by JSPS KAKENHI grant Number 16H06037. We sincerely thank Dr. Yuji Sasaki in Hokkaido University for technical assistance for HR-DSC.

1. Preparation of the Liquid Crystal Alignment Layer of a Perfluoropolymer onto Glass Substrates
<ol>
	<li>Preparation of the perfluoropolymer solution
	<ol>
		<li>Prepare 1 mL of the perfluoropolymer solution by dissolving a perfluoropolymer solution (9 wt% polymer) in a commercial solvent at a ratio of 1:2; this ensures uniform films 0.5-1 &#181;m thick to be spin-coated. 
		NOTE: Please see the Materials List for the solution and solvent used.</li>
	</ol>
	</li>
	<li>Coating of the perfluoropolymer onto clean glass substrates
	<ol>
		<li>Wash the glass substrates (typical size: 1 cm x 1 cm) by sonication at 38 or 42 kHz in an alkaline detergent. Repeatedly rinse them with distilled water. Typically, rinse more than 10 times, with 5 min of sonication each time.</li>
		<li>Subject the substrates to UV-O3 cleaner for 10 min.</li>
		<li>Drip 20 &#181;L of the solution from step 1.1 onto the cleaned glass substrates. Immediately spin-coat the solution at 3,500 rpm and room temperature for 70 s. Bake the film at 80 &#176;C for 60 min to remove the solvent and at 200 &#176;C for 60 min for curing.</li>
	</ol>
	</li>
</ol>
2. Preparation of LC Cells
<ol>
	<li>Glue two glass substrates coated with film together using a photo-curable resin and an LED lamp with a wavelength of 365 nm (1.1 W/cm2). Adjust the thickness of the gap between the two substrates to within the range of 2-100 &#181;m by using micrometer-size glass particles or polyethylene naphthalate films.</li>
	<li>Introduce an LC material, 4&#39;-butyl-4-heptyl-bicyclohexyl-4-carbonitrile (CCN47; 0.2-10 &#181;L)9 to the prepared LC cells using a spatula under capillary force at a temperature higher than the isotropic liquid (I)-nematic (N) phase transition temperature. 
	NOTE: CCN47 has a negative dielectric anisotropy, and the phase sequence is Cry 298.6 K SmA 301.3 K N 331.3 K I, where Cry and SmA stand for crystal and smectic A phases. Do not introduce CCN47 in the N phase or SmA phase, because flow-induced alignment would be promoted.</li>
</ol>
3. Sample Characterization
<ol>
	<li>Texture observation by polarizing optical microscopy (POM)10
	<ol>
		<li>Observe the LC cells under POM with 4-100X objective lenses in conjunction with a hot stage to control the sample temperature with &#177; 0.1-K accuracy. Record the textures in more than 5 frames, at even intervals per Kelvin. Use a digital color camera sequentially, both upon cooling and heating in the range of 291-343 K.</li>
	</ol>
	</li>
	<li>Dielectric spectroscopy (DS)11
	<ol>
		<li>Prepare LC cells, with ITO electrodes &#8211; which can have a square or circular shape and can be purchased commercially &#8211; on both substrates. Solder a lead wire to each substrate. 
		NOTE: Please see the Materials List for the substrates used.</li>
		<li>Measure the capacitance or dielectric constant of the LC cells, exactly as used for POM, using a commercial impedance/gain-phase analyzer. Ensure that the state of the samples is equilibrated before each measurement. Measure the time-dependence of capacitance or the dielectric constant of the LC cells by measuring the capacitance of the LC cells manually every 5 min.</li>
		<li>Start the DS measurement only if the capacitance or dielectric constant of the LC cells becomes non-time-dependent.</li>
	</ol>
	</li>
	<li>High-resolution differential scanning calorimetry (HR-DSC)12
	<ol>
		<li>Put the LC cells into a home-made HR-DSC to be examined, exactly as in POM (never use DSC pans). Refer to Reference 12 to design and build an HR-DSC and to learn how to use it. Perform measurements with scan rates of 0.05-0.10 K/min to enhance the minimum temperature resolving power.</li>
	</ol>
	</li>
	<li>Grazing incident X-ray diffraction (GI-XRD)13
	<ol>
		<li>Put either the LC cell (used for POM or DSC) or a sample with a 2 to 5 &#181;L droplet of CCN47 onto a coated substrate on the GI-XRD sample stage, which should be equipped with a temperature controller.</li>
		<li>Equilibrate the sample for more than 10 min at desired temperatures in the range of 291-343 K, both upon cooling and heating.</li>
		<li>Use an incident X-ray beam on the sample, with a minute incident angle around 0.05-0.10&#176;, to extract surface information on molecular orientation and orderings/structures. Swing the incident angle of the X-ray beam to find the optimal incident angle at which the strength of the diffraction is the strongest. Take the measurements at the optimal incident angle. 
		NOTE: Keep in mind that GI-XRD makes it possible to probe interfacial peculiarities on the nanometer scale, thus maximizing the signal from thin layers while minimizing the signal from the bulk. Note that normal XRD geometries, other than GI-XRD, are not surface-sensitive methods, since the X-ray radiation beam has a large penetration depth into materials.</li>
	</ol>
	</li>
</ol>

<ol>
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S., Yokoyama, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Continuous+Anchoring+Transition+in+Liquid+Crystals.">Continuous Anchoring Transition in Liquid Crystals.</a> Nature. 362, 525-527 (1993).</li><li>Senyuk, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+alignment,+anchoring+transitions,+optical+properties,+and+topological+defects+in+the+nematic+phase+of+thermotropic+bent-core+liquid+crystal+A131.">Surface alignment, anchoring transitions, optical properties, and topological defects in the nematic phase of thermotropic bent-core liquid crystal A131.</a> Phys Rev E. 82 (4 Pt 1), 041711 (2010).</li><li>Bechhoefer, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Critical+Behavior+in+Anchoring+Transitions+of+Nematic+Liquid+Crystals.">Critical Behavior in Anchoring Transitions of Nematic Liquid Crystals.</a> Phys. Rev. Lett. 64 (16), 1911-1914 (1990).</li><li>Dhara, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Anchoring+Transitions+of+Transversely+Polar+Liquid-Crystal+Molecules+on+Perfluoropolymer+Surfaces.">Anchoring Transitions of Transversely Polar Liquid-Crystal Molecules on Perfluoropolymer Surfaces.</a> Phys. Rev. E. 79 (6 Pt 1), 60701 (2009).</li><li>Aya, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stepwise+heat-capacity+change+at+an+orientation+transition+in+liquid+crystals.">Stepwise heat-capacity change at an orientation transition in liquid crystals.</a> Phys. Rev. E. 86 (2), 022512 (2014).</li><li>Aya, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermodynamically+Anchoring-Frustrated+Surface+to+Trigger+Bulk+Discontinuous+Orientational+Transition.">Thermodynamically Anchoring-Frustrated Surface to Trigger Bulk Discontinuous Orientational Transition.</a> Langmuir. 32 (41), 10545-10550 (2016).</li><li>Dhara, S., Madhusudana, N. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Physical+characterisation+of+4'-butyl-4-heptyl-bicyclohexyl-4-carbonitrile.">Physical characterisation of 4'-butyl-4-heptyl-bicyclohexyl-4-carbonitrile.</a> Phase Trans. 81 (6), 561-569 (2008).</li><li>Dierking, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Textures of Liquid Crystals. , (2003).</li><li>Perkowski, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Technical+aspects+of+dielectric+spectroscopy+measurements+of+liquid+crystals.">Technical aspects of dielectric spectroscopy measurements of liquid crystals.</a> Opto-Electronics Review. 16 (3), 271-276 (2008).</li><li>Inaba, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nano-watt+stabilized+DSC+and+ITS+applications.">Nano-watt stabilized DSC and ITS applications.</a> J Therm Anal Calorim. 79 (3), 605-613 (2005).</li><li>Leveiller, F., Boehm, C., Jacquemain, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Two-dimensional+crystal+structure+of+cadmium+arachidate+studied+by+synchrotron+X-ray+diffraction+and+reflectivity.">Two-dimensional crystal structure of cadmium arachidate studied by synchrotron X-ray diffraction and reflectivity.</a> Langmuir. 10 (3), 819-829 (1994).</li><li>de Gennes, P. G., Prost, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> The Physics of Liquid Crystals (Second Edition). , (1993).</li><li>Aya, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Critical+Behavior+in+an+Electric-Field-Induced+Anchoring+Transition+in+a+Liquid+Crystal.">Critical Behavior in an Electric-Field-Induced Anchoring Transition in a Liquid Crystal.</a> Phys. Rev. E. 86 (1 Pt 1), 10701 (2012).</li><li>Avrami, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+Phase+Change.+I+General+Theory.">Kinetics of Phase Change. I General Theory.</a> J. Chem. Phys. 7, 1103-1112 (1939).</li><li>Avrami, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+Phase+Change.+II+Transformation-Time+Relations+for+Random+Distribution+of+Nuclei.">Kinetics of Phase Change. II Transformation-Time Relations for Random Distribution of Nuclei.</a> J. Chem. Phys. 8 (2), 212-224 (1939).</li><li>Avrami, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Granulation+Phase+Change,+and+Microstructure+Kinetics+of+Phase+Change.+III.">Granulation Phase Change, and Microstructure Kinetics of Phase Change. III.</a> J. Chem. 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The authors have nothing to disclose.

The 10x POM images taken using a 5-&#181;m LC cell (Figures 1a and b) clearly show that the orientational state of the bulk LC molecules transits between the P and the V orientations upon temperature variation in a first-order manner. This is marked by the domain nucleation and growth processes, with a new orientation differing from the initial orientation by 90&#176;. The transition temperatures upon cooling and heating are 321.5 K and 325.3 K, respectively. Since CCN47 has a birefringe...

In recent years, there has been growing interest in learning how dynamic molecular features and structures of surface molecules in response to external stimuli might affect the bulk orientation of materials in LC states. One example is to use LC biosensors as a new application of LCs1,2. To quantify how many target bio-species are detected, it is important to know how the interfacial LCs that contact adhering target molecules change and evolve, while also detecting and how they transfer/translate their properties into the bulk.
Using models to pursue these answers, we started with systems that have their surface molecular orientation and short-range orderings varying thermodynamically. These systems allow us to correlate the changes in surface orientation and orderings with the resulting bulk orientation in a systematic way. Recently, we found several LC systems that exhibit orientational transitions, where a spontaneous bulk molecular orientation changes with temperature. In principle, orientational transitions can be categorized into either quasi-second-order3,4 or quasi-first-order transition5,6,7,8. The former is accompanied by a continuous bulk molecular reorientation upon changes in temperature, whereas the latter demonstrates a discontinuous one. In this article, we describe an orientational transition in the quasi-first-order manner between the P and the V orientational states. It proceeds in the single nematic (N) phase by changing the temperature. Details will be provided in the Representative Results and the Discussion.
Since orientational change in the bulk should be governed by a change in the surface molecular orientation and short-range orderings, it is apparent that this system can potentially offer insights into how the thermodynamic variation in surface molecular orientation and short-range orderings affects the bulk orientation. In this article, with the goal of understanding the abovementioned issues, we tackled three problems using four complementary methods (i.e., POM, DS, HR-DSC, and GI-XRD): (1) What does the orientational transition look like? (2) Is the orientational transition thermally detectable? (3) Why and how does the orientational transition occur?

<table><tbody><tr><td>CYTOP</td><td>Asahi Glass Co. Ltd.</td><td>CTX-809A</td><td></td></tr><tr><td>Solvent for CYTOP</td><td>Asahi Glass Co. Ltd.</td><td>CT-180 Sol.</td><td></td></tr><tr><td>Alkaline detergent</td><td>Merck KGaA</td><td>Extran MA01</td><td></td></tr><tr><td>NOA61</td><td>Norland Products, Inc.</td><td>#37-322</td><td>Purchasable from Edmund Optics</td></tr><tr><td>AL1254</td><td>JSR Corporation</td><td></td><td>Planar alignment material in self-made cells</td></tr><tr><td>4&amp;rsquo;-butyl-4-heptyl-bicyclohexyl-4-carbonitrile</td><td>Nematel GmbH &amp;amp; Co. KG</td><td></td><td>Custom-made</td></tr><tr><td>UV-O&lt;sub&gt;3&lt;/sub&gt; cleaner</td><td>Technovision Inc.</td><td>UV-208</td><td></td></tr><tr><td>Hot-stage system</td><td>Mettler Toledo</td><td>HS82</td><td></td></tr><tr><td>High-Definition Color Camera Head</td><td>Nikon</td><td>DS-Fi1</td><td></td></tr><tr><td>Impedance/gain-phase analyzer</td><td>Solartron Analytical</td><td>1260</td><td></td></tr><tr><td>Indium Tin Oxide (ITO)-coated substrate</td><td>GEOMATEC Co. Ltd.</td><td></td><td>Custom-made</td></tr></tbody></table>

orientational transition in a liquid crystal triggered by the thermodynamic growth of interfacial wetting sheets

In liquid crystal (LC) physical chemistry, molecules near the surface play a great role in controlling bulk orientation. Thus far, mainly to achieve desired molecular orientation states in LC displays, the "static" surface property of LCs, so-called surface anchoring, has been intensively studied. As a rule of thumb, once the initial orientation of LCs is "locked" by specific surface treatments, such as rubbing or treatment with a specific alignment layer, it hardly changes with temperature. Here, we present a system exhibiting an orientational transition upon temperature variation, which conflicts with the consensus. Right on the transition, the bulk LC molecules experience the orientational rotation, with 90&#176; between the planar (P) orientation at high temperatures and the vertical (V) orientation at low temperatures in the first-order transitional manner. We have tracked thermodynamic surface anchoring behavior by means of polarizing optical microscopy (POM), dielectric spectroscopy (DS), high-resolution differential scanning calorimetry (HR-DSC), and grazing incidence X-ray diffraction (GI-XRD) and reached a plausible physical explanation: that the transition is triggered by a growth of surface wetting sheets, which impose the V orientation locally against the P orientation in the bulk. This landscape would provide a general link explaining how the equilibrium bulk orientation is affected by surface-localized orientation in many LC systems. In our characterization, POM and DS are advantageous by offering information on the spatial distribution of the orientation of LC molecules. HR-DSC gives information about the precise thermodynamic information on transitions, which cannot be addressed by conventional DSC instruments due to limited resolution. GI-XRD provides information on surface-specific molecular orientation and short-range orderings. The goal of this paper is to present a protocol for preparing a sample that exhibits the transition and to demonstrate how the thermodynamic structural variation, both in the bulk and on surfaces, can be analyzed through the abovementioned methods.

POM images, DS data, HR-DSC data, and GI-XRD patterns were collected during temperature variation, especially in the vicinity of the orientational transition upon both cooling and heating.
Figure 1 represents the evolution of the texture made by POM and DS measurements during the POM observation of the orientational transition from the P (V) to the V (P) orientational state during cooling (heating)....

Watch this Scientific Journal Video about Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets at JoVE.com

Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets

Here, we present a protocol to trigger an orientational transition of a liquid crystal in response to temperature. Methodologies are described for preparing a sample in order to observe the transition and the detailed transitional evolution.

In liquid crystal (LC) physical chemistry, molecules near the surface play a great role in controlling bulk orientation. Thus far, mainly to achieve ...

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7.1K Views.  RIKEN Center for Emergent Matter Science (CEMS).  Hier presenteren wij een protocol om een ​​oriënterende overgang van een vloeibaar kristal te activeren in reactie op de temperatuur. Methodologieën worden beschreven voor het bereiden van een monster om de overgang en de gedetailleerde overgangsontwikkeling te observeren. 

Video: Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets

Dry Oxidation and Vacuum Annealing Treatments for Tuning the Wetting Properties of Carbon Nanotube Arrays

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.1,2 These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.2 Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.3-5
The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

This article describes a simple method to fabricate vertically aligned carbon nanotube arrays by CVD and to subsequently tune their wetting properties by exposing them to vacuum annealing or dry oxidation treatment.

In this article, we describe a simple method to reversibly  tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays.  Here, CNT ...

Characterization of Recombination Effects in a Liquid Ionization Chamber Used for the Dosimetry of a Radiosurgical Accelerator

Most modern radiation therapy devices allow the use of very small fields, either through beamlets in Intensity-Modulated Radiation Therapy (IMRT) or via stereotactic radiotherapy where positioning accuracy allows delivering very high doses per fraction in a small volume of the patient. Dosimetric measurements on medical accelerators are conventionally realized using air-filled ionization chambers. However, in small beams these are subject to nonnegligible perturbation effects. This study focuses on liquid ionization chambers, which offer advantages in terms of spatial resolution and low fluence perturbation. Ion recombination effects are investigated for the microLion detector (PTW) used with the Cyberknife system (Accuray). The method consists of performing a series of water tank measurements at different source-surface distances, and applying corrections to the liquid detector readings based on simultaneous gaseous detector measurements. This approach facilitates isolating the recombination effects arising from the high density of the liquid sensitive medium and obtaining correction factors to apply to the detector readings. The main difficulty resides in achieving a sufficient level of accuracy in the setup to be able to detect small changes in the chamber response.

A growing number of radiation therapy devices offer the advantage of delivering the dose through very small beams to the tumor, allowing for increased conformity and higher doses per fraction. Many different detectors can be used for the dosimetry of these small fields. In the present study, the effect of ion recombination is investigated for a liquid ionization chamber using a stereotactic radiation therapy system.

Most modern radiation therapy devices allow the use of very small fields, either through beamlets in Intensity-Modulated Radiation Therapy (IMRT) or via ...

Phase Diagram Characterization Using Magnetic Beads as Liquid Carriers

Magnetic beads with ~1.9 &#181;m average diameter were used to transport microliter volumes of liquids between contiguous liquid segments with a tube for the purpose of investigating phase change of those liquid segments. The magnetic beads were externally controlled using a magnet, allowing for the beads to bridge the air valve between the adjacent liquid segments. A hydrophobic coating was applied to the inner surface of the tube to enhance the separation between two liquid segments. The applied magnetic field formed an aggregate cluster of magnetic beads, capturing a certain liquid amount within the cluster that is referred to as carry-over volume. A fluorescent dye was added to one liquid segment, followed by a series of liquid transfers, which then changed the fluorescence intensity in the neighboring liquid segment. Based on the numerical analysis of the measured fluorescence intensity change, the carry-over volume per mass of magnetic beads has been found to be ~2 to 3 &#181;l/mg. This small amount of liquid allowed for the use of comparatively small liquid segments of a couple hundred microliters, enhancing the feasibility of the device for a lab-in-tube approach. This technique of applying small compositional variation in a liquid volume was applied to analyzing the binary phase diagram between water and the surfactant C12E5 (pentaethylene glycol monododecyl ether), leading to quicker analysis with smaller sample volumes than conventional methods.

Here, we present a protocol to investigate multi-component phase diagrams using externally controlled magnetic beads as liquid carriers in a lab-in-tube approach. This approach can aid in applications that seek to gather further information on phase change in complex liquid systems.

Magnetic beads with ~1.9 &#181;m average diameter were used to transport microliter volumes of liquids between contiguous liquid segments with a tube for ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Chemistry

Preparation of Liquid Crystal Networks for Macroscopic Oscillatory Motion Induced by Light

A strategy based on doped liquid crystalline networks is described to create mechanical self-sustained oscillations of plastic films under continuous light irradiation. The photo-excitation of dopants that can quickly dissipate light into heat, coupled with anisotropic thermal expansion and self-shadowing of the film, gives rise to the self-sustained deformation. The oscillations observed are influenced by the dimensions and the modulus of the film, and by the directionality and intensity of the light. The system developed offers applications in energy conversion and harvesting for soft-robotics and automated systems.
The general method described here consists of creating free-standing liquid crystalline films and characterizing the mechanical and thermal effects observed. The molecular alignment is achieved using alignment layers (rubbed polyimide), commonly used in the display manufacturing industry. To obtain actuators with large deformation, the mesogens are aligned and polymerized in a splay/bend configuration, i.e., with the director of the liquid crystals (LCs) going gradually from planar to homeotropic through the film thickness. Upon irradiation, the mechanical and thermal oscillations obtained are monitored with a high-speed camera. The results are further quantified by image analysis using an image processing program.

The goal of the protocol is to create liquid crystalline polymer films that can mechanically oscillate under continuous light irradiation. We describe in great detail the conception of free-standing films, from the liquid crystal alignment method to the photo-actuation. The experimental protocol applied to prepare this material is broadly applicable.

A strategy based on doped liquid crystalline networks is described to create mechanical self-sustained oscillations of plastic films under continuous ...

Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals

We discuss in this article the experimental measurements of the molecules in liquid crystal (LC) phase using the time-resolved infrared (IR) vibrational spectroscopy and time-resolved electron diffraction. Liquid crystal phase is an important state of matter that exists between the solid and liquid phases and it is common in natural systems as well as in organic electronics. Liquid crystals are orientationally ordered but loosely packed, and therefore, the internal conformations and alignments of the molecular components of LCs can be modified by external stimuli. Although advanced time-resolved diffraction techniques have revealed picosecond-scale molecular dynamics of single crystals and polycrystals, direct observations of packing structures and ultrafast dynamics of soft materials have been hampered by blurry diffraction patterns. Here, we report time-resolved IR vibrational spectroscopy and electron diffractometry to acquire ultrafast snapshots of a columnar LC material bearing a photoactive core moiety. Differential-detection analyses of the combination of time-resolved IR vibrational spectroscopy and electron diffraction are powerful tools for characterizing structures and photoinduced dynamics of soft materials.

Here, we present the protocols of differential-detection analyses of time-resolved infrared vibrational spectroscopy and electron diffraction which enable observations of the deformations of local structures around photoexcited molecules in a columnar liquid crystal, giving an atomic perspective on the relationship between the structure and the dynamics of this photoactive material.

We discuss in this article the experimental measurements of the molecules in liquid crystal (LC) phase using the time-resolved infrared (IR) vibrational ...

Microfluidic Preparation of Liquid Crystalline Elastomer Actuators

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation usually consists in the formation of droplets containing low molar mass liquid crystals at elevated temperatures. Subsequently, these particle precursors are oriented in the flow field of the capillary and solidified by a crosslinking polymerization, which produces the final actuating particles. The optimization of the process is necessary to obtain the actuating particles and the proper variation of the process parameters (temperature and flow rate) and allows variations of size and shape (from oblate to strongly prolate morphologies) as well as the magnitude of actuation. In addition, it is possible to vary the type of actuation from elongation to contraction depending on the director profile induced to the droplets during the flow in the capillary, which again depends on the microfluidic process and its parameters. Furthermore, particles of more complex shapes, like core-shell structures or Janus particles, can be prepared by adjusting the setup. By the variation of the chemical structure and the mode of crosslinking (solidification) of the liquid crystalline elastomer, it is also possible to prepare actuating particles triggered by heat or UV-vis irradiation.

This article describes the microfluidic process and parameters to prepare actuating particles from liquid crystalline elastomers. This process allows the preparation of actuating particles and the variation of their size and shape (from oblate to strongly prolate, core-shell, and Janus morphologies) as well as the magnitude of actuation.

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation ...

Measuring Magnetically-Tuned Ferroelectric Polarization in Liquid Crystals

Materials showing coupling phenomena between magnetism and (ferro)electricity, i.e., magnetoelectric effects, have attracted a great deal of attention due to their potential applications for future device technologies such as sensors and storage. However, conventional approaches, which usually utilize materials containing magnetic metal ions (or radicals), have a major problem: only a few materials have been found to show the coupling phenomena at room temperature. Recently, we proposed a new approach to achieve room-temperature magnetoelectrics. In contrast to conventional approaches, our alternative proposal focuses on a completely different material, a &#34;liquid crystal&#34;, free from magnetic metal ions. In such liquid crystals, a magnetic field can be utilized to control the orientational state of constituent molecules and the corresponding electric polarization through magnetic anisotropy of the molecules; it is an unprecedented mechanism of the magnetoelectric effect. In this context, this paper provides a protocol to measure ferroelectric properties induced by a magnetic field, that is, the direct magnetoelectric effect, in a liquid crystal. With the method detailed here, we successfully detected magnetically-tuned electric polarization in the chiral smectic C phase of a liquid crystal at room temperature. Taken together with the flexibility of constituent molecules, which directly affects the magnetoelectric responses, the introduced method will serve to allow liquid crystal cells to acquire more functions as room-temperature magnetoelectrics and associated optical materials.

In this report, we present a protocol to examine direct magnetoelectric effects, i.e., induction of ferroelectric polarization by applying magnetic fields, in liquid crystals. This protocol provides a unique approach, supported by the softness of liquid crystals, to achieve room-temperature magnetoelectrics.

Materials showing coupling phenomena between magnetism and (ferro)electricity, i.e., magnetoelectric effects, have attracted a great deal of attention due ...

Preparation of Monodomain Liquid Crystal Elastomers and Liquid Crystal Elastomer Nanocomposites

LCEs are shape-responsive materials with fully reversible shape change and potential applications in medicine, tissue engineering, artificial muscles, and as soft robots. Here, we demonstrate the preparation of shape-responsive liquid crystal elastomers (LCEs) and LCE nanocomposites along with characterization of their shape-responsiveness, mechanical properties, and microstructure. Two types of LCEs &#8212; polysiloxane-based and epoxy-based &#8212; are synthesized, aligned, and characterized. Polysiloxane-based LCEs are prepared through two crosslinking steps, the second under an applied load, resulting in monodomain LCEs. Polysiloxane LCE nanocomposites are prepared through the addition of conductive carbon black nanoparticles, both throughout the bulk of the LCE and to the LCE surface. Epoxy-based LCEs are prepared through a reversible esterification reaction. Epoxy-based LCEs are aligned through the application of a uniaxial load at elevated (160 &#176;C) temperatures. Aligned LCEs and LCE nanocomposites are characterized with respect to reversible strain, mechanical stiffness, and liquid crystal ordering using a combination of imaging, two-dimensional X-ray diffraction measurements, differential scanning calorimetry, and dynamic mechanical analysis. LCEs and LCE nanocomposites can be stimulated with heat and/or electrical potential to controllably generate strains in cell culture media, and we demonstrate the application of LCEs as shape-responsive substrates for cell culture using a custom-made apparatus.

We demonstrate the preparation of siloxane-based and epoxy-based liquid crystal elastomers (LCEs) and LCE nanocomposites. The LCEs are characterized with respect to reversible strain, liquid crystal ordering, and stiffness. As a potential application, we demonstrate their use as shape-responsive substrates in a custom device for active cell culture.

LCEs are shape-responsive materials with fully reversible shape change and potential applications in medicine, tissue engineering, artificial muscles, and ...

Bioengineering

High-Contrast and Fast Photorheological Switching of a Twist-Bend Nematic Liquid Crystal

Smart viscoelastic materials that respond to specific stimuli are one of the most attractive classes of materials important to future technologies, such as on-demand switchable adhesion technologies, actuators, molecular clutches, and nano-/microscopic mass transporters. Recently it was found that through a special solid-liquid transition, rheological properties can exhibit significant changes, thus providing suitable smart viscoelastic materials. However, designing materials with such a property is complex, and forward and backward switching times are usually long. Therefore, it is important to explore new working mechanisms to realize solid-liquid transitions, shorten the switching time, and enhance the contrast of rheological properties during switching. Here, a light-induced crystal-liquid phase transition is observed, which is characterized by means of polarizing light microscopy (POM), photorheometry, photo-differential scanning calorimetry (photo-DSC), and X-ray diffraction (XRD). The light-induced crystal-liquid phase transition presents key features such as (1) fast switching of crystal-liquid phases for both forward and backward reactions and (2) a high contrast ratio of viscoelasticity. In the characterization, POM is advantageous in offering information on the spatial distribution of LC molecule orientations, determining the type of liquid crystalline phases appearing in the material, and studying the orientation of LCs. Photorheometry allows measurement of a material&#8217;s rheological properties under light stimuli and can reveal the photorheological switching properties of materials. Photo-DSC is a technique to investigate thermodynamic information of materials in darkness and under light irradiation. Lastly, XRD allows studying of microscopic structures of materials. The goal of this article is to clearly present how to prepare and measure the discussed properties of a photorheological material.

This protocol demonstrates the preparation of a photorheological material that exhibits a solid phase, various liquid crystalline phases, and an isotropic liquid phase by increasing temperature. Presented here are methods for measuring the structure-viscoelasticity relationship of the material.

Smart viscoelastic materials that respond to specific stimuli are one of the most attractive classes of materials important to future technologies, such ...

Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets

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