This work is partially supported by NSF (DMR-1006870) and NASA (NASA-NNX13AQ60G). X. Z. Wang acknowledges support from the Mary Kay O'Connor Process Safety Center (MKOPSC) at Texas A&amp;M University. We also thank Min Shuai for her guidance.

1. Synthesis of &#945;-ZrP Using Hydrothermal Method
<ol>
	<li>Dissolve 6&#160;g of zirconyl chloride octahydrate (ZrOCl2&#183;8H2O) in 3.75&#160;ml deionized (DI) water in a 150 ml round bottom flask.</li>
	<li>Add 48&#160;ml of 15&#160;M phosphoric acid (H3PO4) dropwise to the ZrOCl2 solution prepared in step 1.1 followed by adding 8.25 ml&#160; deionized (DI) water under vigorous stirring.</li>
	<li>Pour resulting gel-like mixture into Teflon-lined pressure vessel of 80 ml volume. Place the vessel into hydrothermal autoclave composed of stainless steel shell and lid, pressure plate and then tighten well.</li>
	<li>Place the hydrothermal autoclave into convection oven at 200 &#176;C for 24 hr.</li>
	<li>After the reaction, allow the hydrothermal autoclave to cool down 8 hr to room temperature under ambient cooling.</li>
	<li>Collect &#945;-ZrP disks in centrifuge tube after cooling using centrifuge at 2,500 x g for 10 min. Collect liquid portion in waste disposal container since the supernatant liquid contains unreacted phosphoric acid which is corrosive.
	<ol>
		<li>Afterwards, add 40 ml of water to &#945;-ZrP, vortex for 1 min and centrifuge at 2,500 x g for 10 min again. Repeat this step 3 times to ensure that all of the acid is washed away.</li>
	</ol>
	</li>
	<li>Dry ZrP-water sticky mixture in oven at 65 &#176;C for 8 hr and then grind it using a pestle and mortar.</li>
</ol>
2. Synthesis of &#945;-ZrP by Reflux Method
<ol>
	<li>Mix 6 g of ZrOCl2&#183;8H2O with 50 ml of 12 M phosphate acid in a 150 ml round bottom flask.</li>
	<li>The mixture prepared in step 2.1 is reflux in oil bath at 94 &#176;C for 24 hr.</li>
	<li>Wash the product with DI water three times following same protocol in step 1.6, and then dried in the oven at 65 &#176;C for 8 hr.</li>
	<li>Grind dried bulky sample into powder using a pestle and mortar, and stock for later use.</li>
</ol>
3. Synthesis of &#945;-ZrP by Microwave-assisted Method
<ol>
	<li>Add 1 g of ZrOCl2&#183;8H2O into 9 ml of 12 M phosphoric acid solution, and stir the resulting mixture well in a 20 ml scintillation vial.</li>
	<li>Pour 5 ml of the above mixture into a 10 ml glass vessel specified for microwave reactor.</li>
	<li>Set reaction temperature at 150 &#176;C, pressure limit at 300 psi and allow the reaction to happen for 1 hr.</li>
	<li>After the reaction, let the glass vessel cool down for about 15 min and then follow the same procedure as in Steps 1.6-1.7 for acid washing and drying of &#945;-ZrP crystals.</li>
</ol>
4. Exfoliation of Layered &#945;-ZrP into Monolayers
<ol>
	<li>Disperse 1 g of &#945;-ZrP into 10 ml of DI water in a 20 ml scintillation vial.</li>
	<li>Add 2.2 ml of TBAOH (40 wt. %) to it and vortex for at least 40 sec. Notice that molar ratio of Zr:TBAOH is kept as 1:1.</li>
	<li>Sonicate the resulting concentrated suspension for 1-2 hr and leave for 3 days to allow full intercalation of TBA+ ions and complete exfoliation of crystals. Optionally, concentrated suspension can be diluted (2 to 3 times dilution) with water to obtain better exfoliation.</li>
	<li>Centrifuge the exfoliated samples at high rotation speed (2,500 x g) for 1 hr to remove partially exfoliated crystals settled at the bottom. Collect the top part (exfoliated ZrP) in another container, and repeat the procedure until no sediment is found.</li>
</ol>

<ol>
	<li>Usuki, A., Hasegawa, N., Kato, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymer-clay+nanocomposites.">Polymer-clay nanocomposites.</a> Adv Polym. 179, 135-195 (2005).</li><li>Varoon, K., 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=Dispersible+Exfoliated+Zeolite+Nanosheets+and+Their+Application+as+a+Selective+Membrane.">Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective Membrane.</a> Science. 334, 72-75 (2011).</li><li>Mejia, A. F., 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=Aspect+ratio+and+polydispersity+dependence+of+isotropic-nematic+transition+in+discotic+suspensions.">Aspect ratio and polydispersity dependence of isotropic-nematic transition in discotic suspensions.</a> Phys. Rev. E. 85, 061708 (2012).</li><li>Bon, S. A. F., Colver, P. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pickering+miniemulsion+polymerization+using+Laponite+clay+as+a+stabilizer.">Pickering miniemulsion polymerization using Laponite clay as a stabilizer.</a> Langmuir. 23, 8316-8322 (2007).</li><li>Clearfield, A., Stynes, J. 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There is nothing to disclose.

The reflux method is a good option for making a smaller size of &#945;-ZrP with a uniform diameter and thickness. Similar to the hydrothermal method, the reflux method is limited by the preparation time. In general, it takes longer time for the crystals to grow.
The longer reaction time required for reflux method may result in nanodisks with a larger size. The average size of exfoliated nanodisks is measured by dynamic light scattering (DLS). In this study, the size of exfoliated ZrP nanodisks...

Discotic colloids are naturally abundant in the form of clay, asphaltene, red blood cells, and nacre. A range of applications in many engineered systems, including polymer nanocomposites1, biomimetic materials, functional membranes2, discotic liquid crystal studies3 and Pickering emulsion stabilizers4 are developed based on discotic colloidal nanodisks. Nanodisks with uniformity and low polydispersity is important for studying phases and transformations of liquid crystals. Zirconium phosphate (ZrP) is a synthetic nanodisks with well-ordered layered structure and controllable aspect ratio (thickness over diameter). Therefore, the exploration of different synthesis of ZrP helps to establish fundamental understanding of discotic liquid crystal system.
The structure of ZrP was elucidated by Clearfield and Stynes in 19645. For the synthesis of layered crystals of ZrP, hydrothermal and reflux methods are commonly adopted6,7. Hydrothermal method gives a good control on size ranging from 400 to 1,500 nm and polydispersity within 25%6, while reflux method gives smaller crystals for the same duration time. Microwave heating has been proven to be a promising method for synthesis of nanomaterials8. However, there are no papers describing synthesis of ZrP based on microwave-assisted route. The effective control over size, aspect ratio, and mechanism of the crystal growth by hydrothermal method was systematically studied by our group6.
ZrP can be easily exfoliated into monolayers in aqueous suspensions, and the exfoliated ZrP have been well established as liquid crystal materials in Cheng&#39;s group3,9-13. So far, exfoliated ZrP nanodisks with various diameters, say different aspect ratios, have been studied to conclude that larger ZrP had the I (isotropic)-N (nematic) transition at lower concentration compared to smaller ZrP3. The polydispersity3, salt9 and temperature10,11 effects on the formation of nematic liquid crystal phase have been also considered. Moreover, other phases, such as sematic liquid crystal phase, have been investigated as well13,14.
In this article, we demonstrate experimental realization of such a colloidal ZrP nanodisks suspension. Layered ZrP crystals are synthesized via different methods, and then are exfoliated in aqueous media to obtain monolayer nanodisks. At the end, we show liquid crystal phase transitions exhibited by this system. A notable aspect of these disks is their highly anisotropic nature that the thickness to diameter ratio is in the range of 0.0007 to 0.05 depending on the size of disks3. The highly anisotropic monolayer nanodisks establish a model system to study phase transitions in the suspensions of nanodisks.

<table border="0" cellpadding="0" cellspacing="0" height="202" width="928">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:209px;">Material</td>
			<td style="width:208px;"></td>
			<td style="width:164px;"></td>
			<td style="width:352px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Zirconyl Chloride Octahydrate</td>
			<td>Fischer Scientific (Acros Organics)</td>
			<td>AC20837-5000</td>
			<td>98% +&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">o-Phosphoric Acid</td>
			<td>Fischer Scientific</td>
			<td>A242-1</td>
			<td>&#62;= 85 %</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Tetra Butyl Ammonium Hydroxide</td>
			<td>Acros Organics (Acros Organics)</td>
			<td>AC176610025</td>
			<td>40% wt. (1.5M)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Name</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Equipment</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Reaction Oven</td>
			<td>Fischer Scientific</td>
			<td>CL2 centrifuge</td>
			<td>Isotemperature Oven (Temperature Upto 350&#160;C)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Centrifuge&#160;</td>
			<td>Thermo Scientific</td>
			<td>Not Available&#160;</td>
			<td>Rotation Speed : 100 - 4000 rpm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Microwave Reactor</td>
			<td>CEM Corporation</td>
			<td>Discover and Explorer SP</td>
			<td>Temp. Upto 300oC, Power upto 300W, Pressure upto 30bar</td>
		</tr>
	</tbody>
</table>

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.

Figure 1a-c show SEM images of &#945;-ZrP nanodisks obtained from hydrothermal, reflux, and microwave-assisted methods, respectively. It was observed that &#945;-ZrP nanodisks show hexagonal in shape and different thickness depending on synthesis conditions and prepared methods. A previously reported study from our group6 suggests that for the crystal growth time 48 hours or above, the edge of the disks become sharper. Usually, the reflux method yields nanodisk...

Watch this Scientific Journal Video about Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals at JoVE.com

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

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 ...

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8.4K Views.  Texas A&M University. 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. 

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

Nucleoside Triphosphates - From Synthesis to Biochemical Characterization

The traditional strategy for the introduction of chemical functionalities is the use of solid-phase synthesis by appending suitably modified phosphoramidite precursors to the nascent chain. However, the conditions used during the synthesis and the restriction to rather short sequences hamper the applicability of this methodology. On the other hand, modified nucleoside triphosphates are activated building blocks that have been employed for the mild introduction of numerous functional groups into nucleic acids, a strategy that paves the way for the use of modified nucleic acids in a wide-ranging palette of practical applications such as functional tagging and generation of ribozymes and DNAzymes. One of the major challenges resides in the intricacy of the methodology leading to the isolation and characterization of these nucleoside analogues.
	
	In this video article, we present a detailed protocol for the synthesis of these modified analogues using phosphorous(III)-based reagents. In addition, the procedure for their biochemical characterization is divulged, with a special emphasis on primer extension reactions and TdT tailing polymerization. This detailed protocol will be of use for the crafting of modified dNTPs and their further use in chemical biology.

The protocol described herein aims to explain and abridge the numerous obstacles in the way of the intricate route leading to modified nucleoside triphosphates. Consequently, this protocol facilitates both the synthesis of these activated building-blocks and their availability for practical applications.

The  traditional strategy for the introduction of chemical functionalities is the  use of solid-phase synthesis by appending suitably modified ...

Exfoliation of Egyptian Blue and Han Blue, Two Alkali Earth Copper Silicate-based Pigments

In a visualized example of the ancient past connecting with modern times, we describe the preparation and exfoliation of CaCuSi4O10 and BaCuSi4O10, the colored components of the historic Egyptian blue and Han blue pigments. The bulk forms of these materials are synthesized by both melt flux and solid-state routes, which provide some control over the crystallite size of the product. The melt flux process is time intensive, but it produces relatively large crystals at lower reaction temperatures. In comparison, the solid-state method is quicker yet requires higher reaction temperatures and yields smaller crystallites. Upon stirring in hot water, CaCuSi4O10 spontaneously exfoliates into monolayer nanosheets, which are characterized by TEM and PXRD. BaCuSi4O10 on the other hand requires ultrasonication in organic solvents to achieve exfoliation. Near infrared imaging illustrates that both the bulk and nanosheet forms of CaCuSi4O10 and BaCuSi4O10 are strong near infrared emitters. Aqueous CaCuSi4O10 and BaCuSi4O10 nanosheet dispersions are useful because they provide a new way to handle, characterize, and process these materials in colloidal form.

The preparation and exfoliation of CaCuSi4O10&#160;and BaCuSi4O10 are described. Upon stirring in hot water, CaCuSi4O10 spontaneously exfoliates into monolayers, whereas BaCuSi4O10&#160;requires ultrasonication in organic solvents. Near infrared (NIR) imaging illustrates the NIR emission properties of these materials, and aqueous dispersions of these nanomaterials are useful for solution processing.

In a visualized example of the ancient past connecting with modern times, we describe the preparation and exfoliation of CaCuSi4O10 and BaCuSi4O10, the ...

Quantitative and Qualitative Examination of Particle-particle Interactions Using Colloidal Probe Nanoscopy

Colloidal Probe Nanoscopy (CPN), the study of the nano-scale interactive forces between a specifically prepared colloidal probe and any chosen substrate using the Atomic Force Microscope (AFM), can provide key insights into physical interactions present within colloidal systems. Colloidal systems are widely existent in several applications including, pharmaceuticals, foods, paints, paper, soil and minerals, detergents, printing and much more.1-3 Furthermore, colloids can exist in many states such as emulsions, foams and suspensions. Using colloidal probe nanoscopy one can obtain key information on the adhesive properties, binding energies and even gain insight into the physical stability and coagulation kinetics of the colloids present within. Additionally, colloidal probe nanoscopy can be used with biological cells to aid in drug discovery and formulation development. In this paper we describe a method for conducting colloidal probe nanoscopy, discuss key factors that are important to consider during the measurement, and show that both quantitative and qualitative data that can be obtained from such measurements.

Colloidal probe nanoscopy can be used within a variety of fields to gain insight into the physical stability and coagulation kinetics of colloidal systems and aid in drug discovery and formulation sciences using biological systems. The method described within provides a quantitative and qualitative means to study such systems.

Colloidal Probe Nanoscopy (CPN), the study of the nano-scale interactive forces between a specifically prepared colloidal probe and any chosen substrate ...

From Constructs to Crystals &#8211; Towards Structure Determination of &#946;-barrel Outer Membrane Proteins

Membrane proteins serve important functions in cells such as nutrient transport, motility, signaling, survival and virulence, yet constitute only ~1% percent of known structures. There are two types of membrane proteins, &#945;-helical and &#946;-barrel. While &#945;-helical membrane proteins can be found in nearly all cellular membranes, &#946;-barrel membrane proteins can only be found in the outer membranes of mitochondria, chloroplasts, and Gram-negative bacteria. One common bottleneck in structural studies of membrane proteins in general is getting enough pure sample for analysis. In hopes of assisting those interested in solving the structure of their favorite &#946;-barrel outer membrane protein (OMP), general protocols are presented for the production of target &#946;-barrel OMPs at levels useful for structure determination by either X-ray crystallography and/or NMR spectroscopy. Here, we outline construct design for both native expression and for expression into inclusion bodies, purification using an affinity tag, and crystallization using detergent screening, bicelle, and lipidic cubic phase techniques. These protocols have been tested and found to work for most OMPs from Gram-negative bacteria; however, there are some targets, particularly for mitochondria and chloroplasts that may require other methods for expression and purification. As such, the methods here should be applicable for most projects that involve OMPs from Gram-negative bacteria, yet the expression levels and amount of purified sample will vary depending on the target OMP.

&#946;-barrel outer membrane proteins (OMPs) serve many functions within the outer membranes of Gram-negative bacteria, mitochondria, and chloroplasts. Here, we hope to alleviate a known bottleneck in structural studies by presenting protocols for the production of &#946;-barrel OMPs in sufficient quantities for structure determination by X-ray crystallography or NMR spectroscopy.

Membrane proteins serve important functions in cells such as nutrient transport, motility, signaling, survival and virulence, yet constitute only ~1% ...

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline elastomers (LCEs) with facile control over network structure and programming of an aligned monodomain. Tailored LCE networks were synthesized using routine mixing of commercially available starting materials and pouring monomer solutions into molds to cure. An initial polydomain LCE network is formed via a self-limiting thiol-acrylate Michael-addition reaction. Strain-to-failure and glass transition behavior were investigated as a function of crosslinking monomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). An example non-stoichiometric system of 15 mol% PETMP thiol groups and an excess of 15 mol% acrylate groups was used to demonstrate the robust nature of the material. The LCE formed an aligned and transparent monodomain when stretched, with a maximum failure strain over 600%. Stretched LCE samples were able to demonstrate both stress-driven thermal actuation when held under a constant bias stress or the shape-memory effect when stretched and unloaded. A permanently programmed monodomain was achieved via a second-stage photopolymerization reaction of the excess acrylate groups when the sample was in the stretched state. LCE samples were photo-cured and programmed at 100%, 200%, 300%, and 400% strain, with all samples demonstrating over 90% shape fixity when unloaded. The magnitude of total stress-free actuation increased from 35% to 115% with increased programming strain. Overall, the two-stage TAMAP methodology is presented as a powerful tool to prepare main-chain LCE systems and explore structure-property-performance relationships in these fascinating stimuli-sensitive materials.

A novel methodology is presented to synthesize and program main-chain liquid-crystalline elastomers using commercially available starting monomers. A wide range of thermomechanical properties was tailored by adjusting the amount of crosslinker, while the actuation performance was dependent on the amount of applied strain during programming.

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid crystals (ILCs). Taking advantages of the high specificity of XB for haloperfluorocarbons and the ability of anions to act as XB-acceptors, we obtained supramolecular complexes based on 1-alkyl-3-methylimidazolium iodides and iodoperfluorocarbons, overcoming the well-known immiscibility between hydrocarbons (HCs) and perfluorocarbons (PFCs). The high directionality of the XB combined with the fluorophobic effect, allowed us to obtain enantiotropic liquid crystals where a rigid, non-aromatic, XB supramolecular anion acts as mesogenic core.
X-ray structure analysis of the complex between 1-ethyl-3-methylimidazolium iodide and iodoperfluorooctane showed the presence of a layered structure, which is a manifestation of the well-known tendency to segregation of perfluoroalkyl chains. This is consistent with the observation of smectic mesophases. Moreover, all the reported complexes melt below 100 &#176;C, and most are mesomorphic even at room temperature, despite that the starting materials were non-mesomorphic in nature.
The supramolecular strategy reported here provides new design principles for mesogen design allowing a totally new class of functional materials.

A protocol for the synthesis of a new type of mesogens, based on the halogen-bonded supramolecular anion [CnF2n+1-I&#183;&#183;&#183;I&#183;&#183;&#183;I-CnF2n+1]&#8722;, is reported.

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid ...

Facet-to-facet Linking of Shape-anisotropic Colloidal Cadmium Chalcogenide Nanostructures

Here, we describe a protocol that allows for shape-anisotropic cadmium chalcogenide nanocrystals (NCs), such as nanorods (NRs) and tetrapods (TPs), to be covalently and site-specifically linked via their end facets, resulting in polymer-like linear or branched chains. The linking procedure begins with a cation-exchange process in which the end facets of the cadmium chalcogenide NCs are first converted to silver chalcogenide. This is followed by the selective removal of ligands at their surface. This results in cadmium chalcogenide NCs with highly reactive silver chalcogenide end facets that spontaneously fuse upon contact with each other, thereby establishing an interparticle facet-to-facet attachment. Through the judicious choice of precursor concentrations, an extensive network of linked NCs can be produced. Structural characterization of the linked NCs is carried out via low- and high-resolution transmission electron microscopy (TEM), as well as energy-dispersive X-ray spectroscopy, which confirm the presence of silver chalcogenide domains between chains of cadmium chalcogenide NCs.

A protocol detailing how shape-anisotropic colloidal cadmium chalcogenide nanocrystals can be covalently linked via their end facets is presented here.

Here, we describe a protocol that allows for shape-anisotropic cadmium chalcogenide nanocrystals (NCs), such as nanorods (NRs) and tetrapods (TPs), to be ...

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 ...

Exfoliation and Analysis of Large-area, Air-Sensitive Two-Dimensional Materials

We describe methods for producing and analyzing large, thin flakes of air-sensitive two-dimensional materials. Thin flakes of layered or van der Waals crystals are produced using mechanical exfoliation, in which layers are peeled off a bulk crystal using adhesive tape. This method produces high-quality flakes, but they are often small and can be hard to find, particularly for materials with relatively high cleavage energies such as black phosphorus. By heating the substrate and the tape, two-dimensional material adhesion to the substrate is promoted, and the flake yield can be increased by up to a factor of ten. After exfoliation, it is necessary to image or otherwise analyze these flakes but some two-dimensional materials are sensitive to oxygen or water and will degrade when exposed air. We have designed and tested a hermetic transfer cell to temporarily maintain the inert environment of a glovebox so that air-sensitive flakes can be imaged and analyzed with minimal degradation. The compact design of the transfer cell is such that optical analysis of sensitive materials can be performed outside of a glovebox without specialized equipment or modifications to existing equipment.

A method for exfoliating large thin flakes of air sensitive two-dimensional materials and safely transporting them for analysis outside of a glovebox is presented.

We describe methods for producing and analyzing large, thin flakes of air-sensitive two-dimensional materials. Thin flakes of layered or van der Waals ...