LABORATORY EXPERIMENT pubs.acs.

org/jchemeduc

Self-Assembly and Nanotechnology: Real-Time, Hands-On, and Safe Experiments for K-12 Students
Hitesh G. Bagaria, Michelle R. Dean,|| Carolyn A. Nichol, and Michael S. Wong*,,,

Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas 77005, United States Department of Chemistry, Rice University, Houston, Texas 77005, United States Center for Biological and Environmental Nanotechnology, Rice University, Houston, Texas 77005, United States Bellaire High School, Houston, Texas 77401, United States
S b Supporting Information

ABSTRACT: What students and teachers often ask is, how are nano-sized materials made when they are so small? One answer is through the process of self-assembly in which molecules, polymers, and nanoparticles connect to form larger objects of a dened structure and shape. Two hands-on experiments are presented in which students prepare capsules in real time using simple and safe ingredients and study the materials for encapsulation and release of food coloring dye. These experiments are visual and interactive demonstrations of self-assembly (as a synthesis tool) and nanotechnology (in which nanomaterial can be made to perform useful functions), and build on the concepts of acid-base chemistry and electrostatic interaction. KEYWORDS: Elementary/Middle School Science, High School/Introductory Chemistry, First-Year Undergraduate/General, Laboratory Instruction, Physical Chemistry, Hands-On Learning/Manipulatives, Dyes/Pigments, Materials Science, Nanotechnology, Noncovalent Interactions, Acids/Bases

here are many exciting developments in nanotechnology including tunable gold nanoshells for the diagnosis and treatment of disease,1-3 electrically conducing carbon nanowires4,5 that could help solve our energy crisis, and new materials that can be used to inexpensively clean contaminated water.6-8 However, one question that students and teachers often ask is, how are nano-sized materials made when they are so small? One answer is through the process of self-assembly.9,10 To illustrate how molecules and nanoparticles can connect in simple ways to form larger objects of specic shapes, we developed a hands-on experiment to make self-assembled hollow capsules out of nanoparticlesa based on our ndings11 and another procedure based on alginate beads.12 In nature, self-assembly occurs when macromolecules such as cellulose, collagen, and DNA spontaneously form into complex structures through weak intermolecular bonds such as hydrogen bonding, electrostatic, or van der Waals forces. This same process is becoming more appealing as a new approach to making useful materials out of small building blocks as scientists improve their understanding and control of these blocks, and the forces between them, at the nanoscale. Until recently, it has been dicult for scientists to create nano-structured materials with any level of complexity without relying on time-consuming topdown processing such as nanolithography or by moving single
Copyright r 2011 American Chemical Society and Division of Chemical Education, Inc.

atoms with a scanning tunneling microscope. Top-down processes break materials down into smaller and smaller components, whereas bottom-up processes take small molecules or particles and build them up to larger, more complicated structures. The futuristic concept of a device that builds itself from preprogrammed parts (nano-sized or not) should be appealing to students in middle and high school age group. One of the structures that can be built by self-assembly is a microcapsule, a micrometer-sized hollow spherical container that serves to store, protect, and deliver the encapsulated material. These miniature containers are already being used to deliver sunscreen formulations13 and hold promise for several potential applications in medicine.14 The development of a simple and safe method to make microcapsules in the K-12 school laboratory would be a good starting point to introduce nanoscale selfassembly to students. Here we present an example of such a material called nanoparticle-assembled capsules or NACs and demonstrate the encapsulation and release of food colors using them. NACs can be synthesized by a simple two-step mixing process. In the rst step, a salt solution that contains a multivalent
Published: March 14, 2011
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Journal of Chemical Education negatively charged ion (anion) is added to a positively charged (or cationic) polymer solution. The mixing results in crosslinking of the oppositely charged polymer and salt to form polymer-salt aggregates. In the second step, adding a solution of negatively charged nanoparticles (NPs) results in the deposition of NPs on the aggregate to form NACs. Encapsulation is easily achieved by adding the dye prior to addition of NPs. This procedure oers the following benets for easy adaption in the school laboratory: (i) the reagents are commercially available and safe, (ii) the solutions are prepared in water at near-neutral pH and at room temperature, and (iii) the synthesis involves merely mixing the dierent solutions. Many laboratory procedures have been developed to expose chemistry students to the nature of covalent, ionic, and metallic bonding; however, there are few activities that provide insight into weak electrostatic, hydrogen bonds, van der Waals, and dispersive forces. The NAC synthesis protocol will provide students with a hands-on exploration of noncovalent bonding and nanoscale self-assembly. In this work, we use the cationic polymer polyallylamine hydrochloride (PAH), the multivalent anionic salt sodium citrate, and 13 nm silica NPs to demonstrate the encapsulation of food dyes in NACs (1-3 m in size). We examine the release of dyes by two dierent methods. In the rst release method, vinegar (acetic acid) is added to the food dye-encapsulated NACs and the dye is released instantly. This method introduces students to dissociation constants (pKa and isoelectric points), which dictate the charge of molecules at dierent pH values, and its importance in self-assembly. In the second release method, concentrated NaCl solution is added to NACs and a slow diusive release of dye is observed. At high salt concentrations, the attraction between opposite charges (or even the repulsion between like charges) decreases because of the phenomenon called charge screening, an important concept in colloidal science. Finally, we encapsulate food dyes inside millimeter-sized capsules by using the alginate beads of Friedli et al.12 and coating them with a chitosan shell, which can be used as a functional larger-scale model of NACs. The experiments could be integrated into a traditional science lesson, with the connection to nanotechnology as a new point. Criswell recently described a similar approach in this Journal by discussing nanoencapsulation in the context of acid-base chemistry lessons.15 Here, the self-assembly synthesis of capsules would integrate nicely into acid-base lessons also, in which pKa and pH values are important considerations for self-assembly and encapsulation to occur.b

LABORATORY EXPERIMENT

Scheme 1. Flow Diagram Showing the Encapsulation Procedure of Food Dye inside NACs

with denionized (DI) water. The experiments require a centrifuge and a vortex mixer (or magnetic stirrer).
Encapsulation of Food Dyes in NACs

EXPERIMENTAL SECTION
Polyallylamine hydrochloride (PAH, MW = 55 kDa), low viscosity alginic acid sodium salt, low molecular weight chitosan, citric acid monohydrate, sodium acetate trihydrate, ethylenediaminetetraacetic acid tetrasodium salt dihydrate, and calcium chloride were purchased from Sigma-Aldrich. Sodium citrate dihydrate (citrate), sodium phosphate dibasic heptahydrate, sodium chloride, and 1 N HCl solution were obtained from Fisher Scientic. Food dyes (liquid concentrate) and vinegar were purchased from a local grocery store. Silica nanoparticles (Snowtex ST-O) were provided by Nissan Chemicals.16 An alternative to Snowtex ST-O is Ludox AM-30 available from Sigma-Aldrich (product #420875). All solutions were prepared
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Materials

Students are provided with solutions of PAH, citrate, food dye, and silica: (i) 0.1 g of PAH is dissolved in 20 mL of DI water by vigorous shaking, (ii) 0.21 g of sodium citrate dihydrate is dissolved in 50 mL of DI water, (iii) a drop of pink or purple food dye concentrate is added to 100 mL of DI water, and (iv) pH of DI water (45 mL) is adjusted to 3.5 (with 1 N HCl solution) and combined with 3 mL of Snowtex ST-O (20.5 wt %) to obtain a 1.3 wt % silica NP solution.c Students initiate the food dye encapsulation by adding 12.5 mL of citrate solution to 5 mL of PAH solution in a 50 mL centrifuge tube and gently mixing on a vortex mixer (speed 4 of 10) for 10 s. If vortex mixer is not available, the mixing can be done with a magnetic stirrer (speed 4 of 10) for 10 s. The immediate turbidity upon mixing PAH and citrate indicates the formation of PAH-citrate aggregates (Scheme 1). After letting the aggregates sit for 5 min, 12.5 mL of food dye solution is added and the mixture is again stirred gently (speed 4 of 10) for 10 s. Immediately after the dye solution, 12.5 mL of silica NPs solution is poured in and the solution mixed vigorously (speed 8 of 10) for 10 s to form the dye-encapsulated nanoparticle-assembled capsules (NACs). The NACs are left to sit for at least 10 min and then separated by centrifugation (1500g, 10 min) as shown in Scheme 1. The supernatant is discarded and NACs redispersed by adding 10 mL of DI water followed by sonication (if a sonication bath is available) and vigorous mixing.
Release of Food Dyes from NACs

To demonstrate release of the encapsulated food dye, the NAC solution is thoroughly mixed with a pipet and three 2 mL portions are placed in centrifuge tubes. To one centrifuge tube, 2 mL of vinegar (used as received from the store) is added, and to another centrifuge tube, 2 mL of NaCl solution (2.5 g of NaCl in
dx.doi.org/10.1021/ed100598y |J. Chem. Educ. 2011, 88, 609614

Journal of Chemical Education 10 mL of DI water) is added. The third centrifuge tube serves as a control with 2 mL of DI water added.
Encapsulation and Release of Food Dyes from MilliCapsules

LABORATORY EXPERIMENT

Because NACs are too small to see, we developed a second hands-on experiment involving millimeter-sized capsules (millicapsules) for food dye encapsulation and release. Relying on similar charge interactions that drive the self-assembly of the material, this experiment builds on the alginate-bead experimental method published in this Journal.12 The food color is entrapped within alginate-calcium beads (analogous to PAHcitrate aggregates) and the beads are coated by a shell of chitosan molecules (which come from the shells of crabs and other crustaceans). A drop of food dye concentrate is added to 5 mL of alginic acid-sodium salt solution (0.1 wt %) This dye-loaded alginate solution is dropped into a calcium chloride bath (100 mL of 0.5 wt % CaCl2) with a plastic pipet to make 50 beads. The beads are roughly divided into two portions. A chitosan solution is prepared by dissolving 1 g of chitosan in 50 mL of water containing 2 g of citric acid under prolonged stirring. To one portion of the alginate beads, 5 mL of this chitosan-citric acid solution is added. After 5 min, the chitosan solution is removed and replaced with 5 mL of DI water. To the second portion of the alginate beads, only 5 mL of DI water is added. Dye release between the two alginate-bead portions is then compared.

Figure 1. NACs imaged under an optical microscope (left) and a scanning electron microscope (right). The inset in the electron microscope picture shows the high magnication image of the surface of NACs displaying individual silica nanoparticles.

HAZARDS Hydrochloric acid is corrosive and must be used with care. All other chemicals are listed as irritants and must be handled with appropriate personal protective equipment as indicated in the material safety data sheets (MSDS). Although no heating is involved in our experiments, it should be noted that citric acid monohydrate is listed for its ammability hazard. Calcium chloride is noted for its hygroscopic nature and chemical incompatibilities as listed in the MSDS. Being the only nanoparticle-based material, Snowtex ST-O, is relatively safe in the liquid form and is listed as an irritant. In the dried form or as an aerosol, Snowtex ST-O could cause respiratory irritation. For additional safety and hazard information of all chemicals please refer to the MSDS provided by the vendors. RESULTS AND DISCUSSION
Encapsulation of Food Dyes in NACs

the number of citrate molecules attracts more PAH to form bigger aggregates. In fact, by varying the concentration of the polymer and the ratio of citrate-to-polymer, the aggregate size can be varied from a few hundreds of nanometers to micrometers.11,17 Students can vary the citrate-to-polymer ratio to further explore this parameter. In the next step, food dye molecules (all with 2 or more negative charges, Figure S2 Supporting Information) are attracted to the positively charged PAH in the aggregate leading to their encapsulation. In our experiments with dierent colored food dyes, we found that pink and purple dyes could be encapsulated, but not blue and green dyes (Figure S4, Supporting Information). This suggests that factors other than the presence of negative groups such as the geometry of the dye molecule, hydrogen bonding (e.g., DNA base pairing), hydrophobic interactions (e.g., protein structures), or van der Waals forces (dierences in molecular weight) may also be playing an important role. It is also worth noting that the quantity of dye that can be encapsulated is limited by the capacity of the aggregate, just as every vessel has a certain capacity (e.g., a soda can holds 12 oz of beverage and no more). Addition of excess dye will spill out of the aggregates and not result in complete encapsulation. For this study, the quantities of pink and purple dyes were optimized to achieve near complete encapsulation (>90%). Finally, when added, the negatively charged silica NPs (essentially glass) get deposited on the aggregates to complete the encapsulation by forming a shell.
Release of Food Dyes from NACs

The food dye-encapsulated NACs were deposited on a glass slide and imaged under an optical microscope. The circular features in the optical image (Figure 1, left) with an average size of 1.7 ( 0.4 m are the spherical NACs. Because of the limited resolution of an optical microscope, ner structural details of NACs were collected with a scanning electron microscope (SEM) (Figure 1, right). The high magnication SEM inset displays the individual silica nanoparticles that form a NACs shell. The formation of NACs and the encapsulation of food dye can be understood by examining the molecular structure of various components (Figure S1, Supporting Information) and the proposed mechanism shown in Scheme 2. In the rst step, citrate, which has three negative charges, attracts the positively charged PAH polymer, stitching the polymer chains together to form PAH-citrate aggregates. Within a certain limit, increasing
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Addition of vinegar led to instantaneous disassembly of NACs and release of the dye, whereas NaCl encouraged slow release of the food dye (Figure 2). In contrast, the dye remained locked in the control sample where only DI water was added to capsules. These distinct responses to dierent solutions are caused by alteration of the noncovalent bonds. Addition of vinegar causes the pH to drop to about 3. At this low pH, several changes take place. The negative charge of the citrate is almost completely lost and that of the dye is aected depending on the pKa values of the chemical groups. The charge on the silica NPs (which has an isoelectric point of 2.1) also decreases. All these changes cause the capsule structure to collapse resulting in the instantaneous release of the encapsulated food dye. This exercise should be an interesting visual demonstration of the concept of pKa and its importance in self-assembly. In the second release experiment, addition of NaCl solution to the capsules causes the stitch (or the attraction) between PAH and other components (citrate, dye, and silica NPs) to loosen up owing to the phenomenon called charge screening. In simple
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Scheme 2. Schematic Showing the Proposed Mechanism of Formation of Polymer-Salt Aggregates and Encapsulation of Food Dye in NACs

Figure 2. Release of food dye from NACs by the addition of vinegar and NaCl solutions. In the control sample, most of the dye is encapsulated in the capsules (bottom of the tube), whereas in vinegar, signicant quantity of dye is released into the solution. In NaCl, capsules are swollen (bottom of the tube) releasing the dye slowly.

Figure 3. Release of food dye from calcium-alginate beads with and without chitosan shell. Beads with chitosan shell retained most of the dye, whereas beads without chitosan shell released the dye almost completely.

terms, this phenomenon refers to the reduction in electrostatic interactions around charged colloidal particles and polymer (here PAH) in the presence of ions (here NaCl). The reduction in electrostatic interactions results in swollen capsules (see the increased volume of capsule in the NaCl sample in Figure 2), allowing the slow release of dye to take place. Both dissociation constants and charge-screening naturally lead into the fundamental concepts of colloidal science.
Alginate Milli-Capsules

Effect of Salt Valency

In the food dye release experiment with the milli-capsules, it was found that coating with a chitosan shell signicantly prevented release of the food dye compared to beads without the shell (Figure 3). This result serves two purposes: (i) it provides students with a larger functional capsule model, so they better relate to the structure of micrometer-sized NACs and (ii) it also emphasizes that, while nanoscale assembly results in new materials owing to the novel structures, the same traditional laws governing the fundamental forces between molecules (here the noncovalent forces) apply to both small and large assemblies.

PROJECT EXTENSIONS For the more advanced student (high school or rst-year undergraduate), the NACs activity can be modied to further students understanding of self-assembly. Two examples are given.
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An important prerequisite to formation of NACs is the ionic cross-linking between the cationic polymer and the multivalent anionic salt to form polymer-salt aggregates (Scheme 1). Multivalency of the salt is essential for this ionic cross-linking. In this project extension, teachers could demonstrate the eect of changing the salt valency with the following salts: (i) ethylenediaminetetraacetic acid tetrasodium salt dihydrate (EDTA, 4 negative groups), (ii) sodium citrate dihydrate (citrate, 3 negative groups), (iii) sodium phosphate dibasic heptahydrate (phosphate, 2 negative groups), and (iv) sodium acetate trihydrate (acetate, 1 negative group). Molecular structures of these salts are shown in Figure S6 (Supporting Information). Replacing the citrate solution (0.21 g in 50 mL water) with either EDTA (0.22 g in 50 mL of water) or phosphate (0.29 g in 50 mL of water) will result in turbidity, indicating formation of polymer aggregates (Figure 4). However, when replacing with acetate (0.29 g in 50 mL of water), turbidity is not observed, indicating no aggregate formation. Although dierent quantities of other salts are used, the overall R ratio (dened as the total number of negative groups from the salt in solution divided by the total number of positive groups from the polymer in solution) is the same in all cases here. These observations show the importance of multivalency, and indicate how the salts need to have multiple charges to
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forces and their importance in nanoscale self-assembly. Students are also introduced to dissociation constants and charge screening, which dictates some of these forces and which are fundamental to colloidal science. For the more advanced student, modication of the synthesis method can be readily performed to explore the limits and possibilities of self-assembly and encapsulation by studying and understanding the eects of dierent synthesis parameters (e.g., the valency of the anionic salt, salt-polymer ratio, pH, and dierent types of dyes, polymer, and nanoparticles).

ASSOCIATED CONTENT
S b

Supporting Information Physical properties of Snowtex ST-O; Cost of chemicals; Structure of chemicals used for synthesis of NACs; Food dye structure and composition; Encapsulation of dierent colored dyes in NACs; Structure of alginic acid and chitosan used in synthesis of alginate milli capsules; Chemical structure of anionic salts for the Eect of salt valency project extension. This material is available via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author

*E-mail: mswong@rice.edu.
Figure 4. (A) Schematic structure of the positively charged polyallylamine hydrochloride (PAH) and negatively charged salts with dierent valencies: acetate, phosphate, citrate, and etheylenediaminetetraacetate (EDTA). (B) Photograph of the mixtures of PAH and salts at xed salt to polymer charge ratio (R = 2). Clear solution for PAH-acetate mixture shows no aggregates are formed. Turbidity in all other solution with higher-valent salts (phosphate, citrate, and EDTA) indicates successful aggregate formation by ionic cross-linking as depicted by drawings at the bottom.

bind to multiple chains. Further information on these experiments is available from our earlier work.11,17,18
Effect of R Ratio

Another important parameter in the assembly of polymer-salt aggregates is the R ratio itself. The NACs synthesis described in this work uses a R ratio of 2. To study the eect of this parameter, the polymer concentration can be kept constant (0.1 g of PAH is dissolved in 20 mL of water) while changing the concentration of citrate. It is found that when R is very low (for example, 0.021 g of citrate in 50 mL of water, to give R = 0.2) there is not enough citrate to cross-link the polymer chains, as observed by the absence of turbidity. When R is near 1 (as already seen with 0.21 g of citrate in 50 mL of water, to give R = 2), enough aggregates are formed to turn the solution cloudy. Finally, when R is much greater than 1 (for example, 2.1 g of citrate in 50 mL of water, to give R = 20) crosslinking, and cloudiness, happens very rapidly.

ACKNOWLEDGMENT We acknowledge Atsushi Muto from the Naka Application Center at Hitachi High-Technologies Corporation, Japan for collecting high-resolution scanning electron microscope images of the capsules, and Douglas Natelson (Rice University) and Shyam B. Kadali (Rice University) for helpful discussions. We thank the entire DragonFlyTV team (Twin Cities Public Television, St. Paul, Minneapolis), especially Angie Prindle, Lauren Dittmer, and Lisa Regalla. Tara Lang (Childrens Museum of Houston) is thanked for her coordination eorts. This work was made possible by support from NSF (EEC-0647452, Center for Biological and Environmental Nanotechnology; CBET-0652073, MSW), 3M (NTF Award, MSW), the Methodist Hospital Research Institute, and the Sid W. Richardson Foundation (Institute of Biosciences and Bioengineering Medical Innovations Award Grant, MSW). ADDITIONAL NOTE a This experiment was the subject of a nanoscience segment on the Public Broadcasting Station (PBS) show entitled Dragony TV, which highlighted a new exhibit at the Houston Childrens Museum on the topic of self-assembly.19 The procedure was an outcome of the Center for Biological and Environmental Nanotechnologys Research Experience for Teachers and represents our eorts to disseminate nanotechnology research (based on self-assembly and physical chemistry concepts developed by us) for K-12 education.
Teachers could show the Dragony TVs self-assembly video freely available on the PBS Web site,19 followed by hands-on experimentation as described in this work. Although all activities in this work have been performed with Snowtex ST-O, Ludox AM-30 (30 wt %) may also be used instead. Ludox AM-30, supplied at pH of 8.9, should be diluted to 1.3 wt % level with DI water and adjusted to pH 3.5 with 1 N HCl.
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CONCLUSIONS The hands-on experiments presented here introduce the vast and cutting edge area of nanoscale self-assembly to students by a very simple and safe method called the nanoparticle-assembled capsules or NACs. The ease of synthesizing NACs and access to reagents used here encourages students to not only develop interest for science, but also explore their ideas. In particular, the experiments allow students to learn about noncovalent forces such as electrostatic, hydrogen bonding, van der Waals, and dispersive

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