Lesson Plan. Properties of Colloidal Metals on the ano Scale

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1 Lesson Plan Properties of Colloidal Metals on the ano Scale Example: Colloidal Gold Objectives: 1. Through an illustrative experiment gain an understanding that nano size leads to changes in optical properties of materials 2. Use the color wheel to explain the color of the gold colloid 3. Relate the direction of color change to basic physical principles (light absorption and harmonic motion) 4. Motivate students to explore applications of this unique phenomenon Materials Gold colloid solution (provided) 0.5 M sodium chloride (NaCl) Red food coloring solution Test tubes Droppers Laser pen Prism Model of simple cubic structure 60 ml (2.92 grams NaCl/100mL water) Preparatory Work 1. Assignment: Have students investigate the nature of white light 2. Using a prism, demonstrate that white light is composed of the spectrum. Use the laser pen to demonstrate the difference between monochromatic and white light. 3. Discuss wavelength 4. Discuss the color wheel and the relationship of absorbed light to the color of an object (If covered earlier in your regular class, review with class or assign review prior to class.) 1

2 5. View animation (optional) Development Sequence (detailed steps to perform classroom activity together with explanations and exercises) 1. Explain Nano size: Micron, Nanometer, Angstrom 2. Describe colloids and distinguish between colloids, suspensions, and solutions. (see Appendix) 3. Explain how gold colloid is formed; observation of colloid 4. Why is the colloid red? Teacher will discuss colors using the prism and light absorption. What is white light? 5. Teacher will explain ion compounds, crystal structure, electromagnetic waves, resonance, light absorption in solids 6. Demonstration of Tyndall Effect. 7. Observation of color of colloidal gold; class to perform experiment adding NaCl and recording changes 8. Teacher will explain reason for color and color change 9. [2 nd period]-teacher will explain the principles of the UV-VIS spectrometer and perform remote demonstration of light absorption in colloidal Au samples. The spectrometer will be accessed for the classroom through the NTEN internet portal. (Instructions will be supplied separately; the teacher will do a trial run prior to the lesson). 2

3 Color wheel The color wheel shows complementary colors. If a color is absorbed, the color opposite it on the wheel is observed nm nm nm nm nm nm The labels indicate the wavelength of the light in nanometers (nm). 3

4 Warm-up exercise Use the Tyndall effect (see in the gold colloid solution & food colored water to illustrate colloid properties. This may help in answering the students question, How do I know that there are gold particles? Also, explain how the colloidal gold is produced (see Appendix I). Shine the light beam through the food colored distilled water, then through the colloidal gold solution. Note that the beam is not visible in the food colored solution, but appears as a line in the colloidal gold solution. Question: What accounts for the difference? Experimental Procedure: 1. Add 1M NaCl solution to the red colloidal gold solution dropwise, gently shaking. Do this slowly. Wait several minutes between drops and observe the color. The color should transition from red to blue and then become clear as the particles get so large that they begin to precipitate out. 2. Use the table below to record the color vs. time Color Time For teacher--au particle size Red 15 nm Red-purple Purple 40 nm Blue Dark blue 100 nm Blue-gray gray clear Precipitated out of solution (may be able to see fine particles at bottom of test tube). The particles will appear dark, not gold color, because they are still small, but not small enough that nano effects occur. Explanation: The size of the nanoparticle is such that the natural vibration (resonance) frequency of incident light is in the green, so that green light is absorbed. The transmitted light is the complement of this, or red. See below for full explanation. I. Reasons for color change with acl addition: Increase in particle size 4

5 Because of the way in which the gold colloid is made, each 15nm nanoparticle has a negative charge. This repulsion keeps that particles separated and stabilizes their size. Addition of NaCl, which in solution is ionic, reduces the negative charge and allows the particles to aggregate and grow larger. The applet below illustrates how charged particles interact. Select as examples: 1. Single negative charge. a. Move the + test charge around, the arrow indicates the force on the charge. Note that when it is near the charge, the force arrow points toward the charge (attraction) 2. Single positive charge a. Again, move the + test charge around, the arrow indicates the force on the charge Note that when it s near the + charge, the force arrow points away from the + charge (repulsion) 3. Two equal negative charges. Observe field lines & note direction of arrows (repulsion). 4. Equal unlike charges. Observe attractive field lines. II. Explanation for color change: Change in light absorption with particle size Light consists of electromagnetic waves. Light waves, like waves in water, can be described by the distance between two successive peaks of the wave - a length known as the wavelength (λ). The color of the light that we observe depends on the wavelength and is shown in the color wheel figure. The gold that we study has electrons that are free to move throughout the material. These electrons are called conduction electrons, have a negative charge, and are the carriers of electricity. Light striking the metal interacts with the electrons, causing them to oscillate in sync with the wave (harmonic motion). Harmonic Motion Harmonic motion can be illustrated using an example of a mass on a spring. See applet at: (mass on a spring) 5

6 To use applet: 1. Move mass up a small amount 2. Set mass at 1 kg, push Start, the mass on the spring will oscillate and the curve depicts the mass position 3. Let curve go until it stops 4. Set mass at 9 kg, push Start 5. The 9 kg curve will overlay the first This applet shows the motion of a mass connected to a spring. We apply a force to initially stretch the spring and the mass then moves up and down as the spring is regularly stretched and compressed. The spring always produces a force opposite to the motion of the mass. This is called a "restoring force since it always acts to bring the spring back through the starting position. Application to Colloidal Gold Analogous to the mass moving in response to the spring, the electrons in the gold move in a similar way in response to the lightwave. The force produced by the lightwave moves the electrons away from their equilibrium (normal) positions while the electrostatic forces of the nucleus (positively charged) pulls them back (restoring force). Every system subject to this type of motion, called harmonic motion, has a natural or resonant frequency of vibration. The applet shows this for masses of 1kg and 9kg in which the mass 1kg vibrates much more rapidly than does the mass 9kg. Now consider a child on a swing and the way that you push it. Instead of pushing at random, you push the swing down when it reaches its highest point so that it absorbs the maximum amount of your energy and continues to go higher. You are pushing at the resonant frequency and the swing is then said to resonate. In the same manner, the electrons in the metal resonate upon application of light of their characteristic frequency. There is a difference, though, between bulk and nano gold. Since bulk gold s dimensions are much larger than the wavelength of the light, different regions of the gold see different portions of the lightwave and the electrons don t oscillate together. However, for nanoparticles, the entire material is bathed in light whose wavelength of ~500nm is much larger than the 15nm Au particle size. Because of this, resonance occurs, the electrons oscillate together (collectively), and the light is absorbed in the same way that your energy is absorbed when pushing the swing. Scientists have calculated the relationship between the radius of the nanoparticle and the wavelength of the light that is absorbed. They find that the wavelength is proportional to 6

7 the square of the particle diameter (λ~ D 2 ) 1. In other words, as the particle gets larger, the wavelength of the absorbed light increases. This agrees with what we found in the experiment; the color of the colloid particle depends on its size. With increasing size (aggregation caused by addition of sodium chloride), the absorbed light moves toward the longer wavelength, the red, and the observed color (from the color wheel) moves toward the blue. 1. What would we observe if green light were shone on the colloid solution rather than white (or red)? 2. Demonstrate color change on addition of NaCl. Why does it change? Why does it move toward the blue? 3. Why does the color continue to change with time? 4. Demonstrate remote use of the UV-Vis spectrometer [2 nd period] 5. Assignments: a. Research the difference between solution, colloid, and suspension b. Find examples of the use of this unique nano property (the ability to adjust the frequency (color of the light absorbed in the nanoparticle) 6. For teachers: relate this experiment to standards (need teacher input to this) III. Applications A. There are a number of fascinating applications to cancer treatment that involve selective absorption of light by nanoparticles. They are found in the links below Rayford, Schatz, Shuford, Nanoscape, v.2, Issue 1, Spring

8 B. Cisplatin is a drug that treats cancer successfully. Unfortunately, the drug can harm healthy cells as well as cancerous ones. Nano gold particles combined with DNA can deliver drugs directly to where they are needed inside a patient s body. Once inside the cancer cells, cisplatin is then released, selectively killing the cancer cells. C. Another example is zinc oxide used in sunscreens. When the particles are large, they are the familiar white. However, zinc oxide nanoparticles are transparent to visible light, but completely absorb UV light. See below and note the last slide 6-S5. tudent.pdf D. Nanoparticles can be designed to transduce microwave radiation into heat. Such methods of focused microwave thermotherapy could be used in the treatment of BPH, prostate cancer and other types of cancer. The nanoparticles can be designed for optimal heat production response at specific microwave frequencies and/or ranges of microwave frequencies spanning the entire microwave spectrum. E. Historic Uses Nanoparticles effects have been seen and uses for centuries. One example of this the red color in stained glass windows. Medieval artisans mixed different compounds (like gold chloride and other metal oxides and chlorides) into the molten glass. When they added the gold chloride, it turned the glass a rich ruby red. Although they didn t know why the color resulted, this is now understood. Cf. Assignment: Identify other historic uses of nano-metals IV. Correlation to PA Academic Standards Grade PA Academic Standard Description Correlation to anotechnology Course 8

9 A Structure & prop. of matter, solutions, mixtures B Instruments to study materials D Scale as relating to concepts Metals, insulators, semiconductors, colloids Tele-experimentation. The nano scale & its consequences A scale Use of the Powers of Ten A Concepts re structure of matter B Instruments/apparatus to examine objects & processes to illustrate nano scale Metals, insulators, semiconductors, new effects at nanoscale Tele-experimentation using university equipment D Analysis of scale Nano scale B,C Atomic structure, chem. Effect of size, metal colloids reactions, solutions A Atomic & molecular bonds Dipoles-atomic force microscope, semiconductors, QDots A solutions Metal colloids C1 Pendulum, simple Atomic forces, vibrations harmonic motion Formative Assessment 1. Give a short quiz in class or a take-home quiz 2. Have students write for one/two minutes on what they thought was the most important information that they learned Practice/Reinforcement 1. Assign the pendulum; relate to mass on a spring (harmonic motion) 2. Have students read Feynman lecture, There's Plenty of Room at the Bottom, An Invitation to Enter a ew Field of Physics Have students identify other means of color change, e.g., indicators, iodine/starch and discuss differences between them and the nano experiment (colloid, solution) 4. Investigate preparation of colloidal metals, specifically gold and silver. How do we get such small particles in solution? 5. Investigate methods of measuring particle size V. References 9

10 J. Turkevich, P. C. Stevenson, J. Hillier, "A study of the nucleation and growth processes in the synthesis of colloidal gold", Discuss. Faraday. Soc. 1951, 11, A. D. McFarland, C. L. Haynes, C. A. Mirkin, R. P. Van Duyne and H. A. Godwin, "Color My Nanoworld," J. Chem. Educ. (2004) 81, 544A. J. Kimling, M. Maier, B. Okenve, V. Kotaidis, H. Ballot, A. Plech, "Turkevich Method for Gold Nanoparticle Synthesis Revisited", J. Phys. Chem. B 2006, 110, S. Solomon #24, Study of Colloidal Gold Solution, (2006) 10

11 Appendix I: Preparation of 15 nm-diameter Gold anoparticles The preparation relies on the chemical reduction of tetrachloroauric acid by sodium citrate. The sodium citrate reduces the Au ions to nanoparticles of Au metal. Excess citrate anions in the solution adhere to the Au metal surface, giving an overall negative charge to each Au nanoparticle. Materials ml Erlenmeyer flask 2. Magnetic stir bars 3. Two (2) Stirring hot plates 4. HAuCl 4 solution 5. Sodium citrate solution 6. Distilled water Process For each batch of colloidal gold: 1. Dilute 25mL of the HAuCl 4 solution to 250mL in a clean 500mL Erlenmeyer flask. 2. Mark the liquid level. 3. Heat to boiling with vigorous stirring. Use a watch glass to minimize evaporation. 4. Add 25mL of the sodium citrate solution all at once with vigorous stirring. The yellow solution turns clear, dark blue, then a deep red-burgundy color within a few minutes. 5. Stir and boil for 15 min after red color appears. 6. Cool: Remove from heat, move to another stirring plate and continue stirring for 15 min. 7. Since some liquid is lost by evaporation, add water to bring to 250mL 8. When cooled to room temperature, store in an amber bottle 9. The shelf life of the colloidal gold is more than 6 months 10. Store the unused HAuCl 4 solution in an amber bottle Appendix II: UV-Vis Spectrometer Operation A diagram of the components of a typical spectrometer is shown in the following diagram. The functioning of this instrument is relatively straightforward. A beam of light from a visible and/or UV light source (colored red) is separated into its component wavelengths by a prism or diffraction grating. Each monochromatic (single wavelength) beam in turn is split into two equal intensity beams by a half-mirrored device. One beam, the sample beam (colored magenta), passes through a small transparent container (cuvette) containing a solution of the compound being studied in a transparent solvent. 11

12 The other beam, the reference (colored blue), passes through an identical cuvette containing only the solvent. The intensities of these light beams are then measured by electronic detectors and compared. The intensity of the reference beam, which should have suffered little or no light absorption, is defined as I 0. The intensity of the sample beam is defined as I. Over a short period of time, the spectrometer automatically scans all the component wavelengths in the manner described. The ultraviolet (UV) region scanned is normally from 200 to 400 nm, and the visible portion is from 400 to 800 nm. Note to remote demonstration: The spectrometer absorption scale is logarithmic: 0 represents 1, 1 represents 10, 2 represents 100, and 3 represents In spectroscopy, the absorbance A is defined as, where I is the intensity of light at a specified wavelength λ that has passed through a sample (transmitted light intensity) and I 0 is the intensity of the light before it enters the sample or incident light intensity. 12

13 Appendix III: Solutions and mixtures Types of Mixtures Homogeneous mixtures are uniform throughout. The composition is the same in all directions in the substance. The types of particles observed in one direction are the same that are observed in all others. A solution of sugar in water is homogeneous. Heterogeneous mixtures are not uniform. There are pockets of one substance surrounded by pockets of different substances. A mixture of soil in water to make "mud" is heterogeneous. Likewise a mixture of oil and water in salad dressing is heterogeneous. Types of Homogeneous Mixtures Solutions Particle sizes distinguish one homogeneous mixture from another. Solutions are mixtures with particle sizes at the molecule or ion level. The particles have dimensions between 0.1 to 2 nanometers. Typically solutions are transparent. Light can usually pass through the solution. If the solute is able to absorb visible light then the solution will have a color. A blue liquid transmits blue light and absorbs the other colors of the spectrum. A solution may have a "color" but it will still be transparent. A mixture of water and sodium chloride is homogeneous by chemistry standards. The particles in the mixture are molecules of H 2 O and hydrated sodium cations, Na +, and chloride anions, Cl -. Solutions are transparent. You can see through them. The mixture remains stable and does not separate after standing for any period of time. The particles are so small they cannot be separated by normal filtration. Colloids Colloids are mixtures with particle sizes that consist of clumps of molecules. The particles have dimensions between 2 to 1000 nanometers. The colloid looks homogeneous to the naked eye. Fog and milk are examples of colloids. Colloids frequently appear "murky" or "opaque". The particles are large enough to scatter light. You have experience with the way fog interacts with the light from car headlights. Colloids generally do not separate on standing. They are not separated by filtration. Suspensions Suspensions are homogeneous mixtures with particles that have diameters greater than 1000 nm, meter. The size of the particles is great enough so they 13

14 are visible to the naked eye. Blood and aerosol sprays are examples of suspensions. Suspensions are "murky" or "opaque". They do not transmit light. Suspensions separate on standing. The mixture of particles can be separated by filtration. 14

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