Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin Howard University gharris@msrce.howard.edu & jagriffin@howard.edu Cancer and the way in which we treat cancer is about to change forever. Imagine if you were informed when the first cell in your body became cancerous. Doctors could almost guarantee a speedy recovery and cure. Nanotechnology will allow us to act on information like this. Today the heart of a computer is based on what is called transistor technology and building these transistors requires “top down” technology (carving transistors out of pieces of silicon using lithography techniques). How about assembling computers using individual molecules and atoms? Clearly, these computers would be smaller and thereby faster. Specific manipulation of surfaces for new effects and improvement of surface properties are leading to corrosion protection (the deterioration caused by chemical reaction with the environment, affects materials as different as structural metals, ceramics, and wood, as well as works of art and artifacts from past civilizations), abrasion resistance (no superficial damage to the surface at all), photo-catalysis (this technique utilizes nanosize particles to carry out oxidation to disassemble volatile organic compounds into common gases), and antigraffti surfaces (surfaces that can’t be painted or written on) that have added new functionality though nanotechnology. Nanotechnology is the understanding and control of matter at dimensions of roughly 1 to 100 nanometers, where unique phenomena enable novel applications [1]. A nanometer is one billionth of a meter. The prefix “nano” comes from a Greek word meaning dwarf. Encompassing nanoscale science, engineering and technology, nanotechnology involves imaging, measuring, modeling, and manipulating matter at this length scale. There is no field of science and engineering that is not impacted by nanotechnology. Atoms and molecules are the building blocks of all matter. Matter “Atoms are letters. Molecules are the words” [2]. All stuff or matter is composed of atoms. Matter is defined as anything that has mass and occupies space. There are three basic forms of matter: solid, liquid and gas. Solids include things like glass, metal, stones and rocks. They are fixed in shape and occupy space. Liquids such as water, soda, oil and alcohol also occupy space, but their shape changes depending on the shape of the vessel in which they are stored. Gases such as air, helium, and natural gas seem to Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 1 of 8 occupy no space, but they have both mass and volume. To make things interesting, some things like water commonly exist in all three forms or states (water, ice and steam). The unique character of the way matter reacts with other matter is due to their properties. These properties are grouped into two classes: physical and chemical. Physical properties are special characteristics that make up the physical composition of a sample. These properties can also change at the nano level. Physical properties include: form, density, thermal and electrical conductivity, melting and boiling point, etc. Chemical properties are those characteristics that focus on the substance’s behavior when mixed with different elements or compounds. Chemical properties are also a function of the size of the elements. Nanosize particles react differently. Size and scale often affect how matter behaves in surprising ways. As size or scale approach the nano-region, behavior is difficult to predict using classical theory. Atoms are the smallest unit of substances and these atoms are in constant motion and interact with other atoms to form molecules. The arrangement of these building blocks gives materials their many properties like mechanical strength, ability to conduct electricity, melting point, etc. An atom is composed primarily of three fundamental parts: electrons, protons and neutrons. The combination of these parts and the number of these parts is unique for every element known to exist in the universe. Each element has a known unique number of protons and electrons. Protons are particles with a positive (plus) charge. Electrons are particles with a negative (minus) charge. Under normal conditions an atom is neutral (equal number of positive and negative charges). An element with five protons is boron. How many electrons must it have to be neutral? The answer is five. The Elements The Periodic Table of Elements is a very useful table for describing the atoms of every known element. The lightest elements are hydrogen and helium. All the heavier elements are made, both naturally and artificially. Every known element has a nickname, which consist of one-to-two letters. For instance, C is the nickname for carbon. An atom of carbon has six protons and six electrons. The number of protons in an atom of an element is called its atomic number. The Periodic Table of Elements can be used to determine the number of electrons in a neutral atom of copper (Cu). Neutrons are large and heavier than electrons and protons and have no electrical charge. Since the total charge of an atom is zero, an atom normally has an equal number of electrons and protons under normal conditions. Not all atoms of the same element have the same mass. These different forms of the same element are known as isotopes. For instance, carbon12 and carbon-13 both have six protons and six electrons, but the number of neutrons in each is 6 and 7 respectively. Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 2 of 8 The nucleus is where the protons and neutrons hang out. Sometimes this nucleus can behave like a small magnet and line-up in a magnetic field. This magnetic property of the nucleus is called the magnetic moment and is important in detecting these nuclei when using a magnetic field. The elements of the periodic table are placed in specific rows and columns because of the way they look and act. If you have ever looked at a grid, you know that there are rows (left to right) and columns (up and down). The periodic table has rows and columns, too, and each one means something different. Each row in the table is considered to be a different period. Elements have something in common if they are in the same row. All of the elements in a column have the same number of outer electrons. A Danish physicist, Neils Bohr, came up with a model that pictured the atom with a nucleus made up of protons and neutrons in the center and electrons spinning in an orbit around it, like the Sun and Planets. The electron, which is 1836 times lighter than the proton, has a negative charge and the proton has an equal positive charge. Remember that the third subatomic particle, the neutron has no charge but is heavier than both the electron and proton. According to Bohr’s Theory, an orbit is the path that an electron follows as it moves around the nucleus. The orbits appear as a series of concentric circles with their centers located at the nucleus. The Bohr model for hydrogen (H) is shown below. The simple Bohr Model has evolved because small subatomic matter has something called duality. That is to say that atomic and subatomic matter can act like both waves and particles. This field of study is called quantum mechanics and is a theoretical mathematical approach to the study of atomic and molecular structures. Quantum Mechanics is a very complex theory. Classical mechanics has its foundation in Newton’s Laws of Motion. Classical mechanics does a great job of describing and predicting things at the macroscopic scale (large world view). This would include things like cars, trains, bullets, football flight, etc. These laws can describe things that you can see with the naked eye. However, when things get small like on the nanoscale size (10-9 m or one billionth of a meter), Newton’s Laws of Motion do not predict the behavior of this type of matter. The point at which an aggregation of particles becomes more accurately described by classical physics than by quantum mechanics is known as the classical limit. Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 3 of 8 The wave properties of matter form the basis of quantum mechanics. The term “quantum mechanics” is used because wave mechanics predicts only certain allowed energies, called quantum states. In the ocean, the wind produces waves whose crests and troughs move across the water. The distance between the peaks of the waves is called the wavelength (λ). The waves also have height and frequency. These are examples of traveling waves. DeBroglie proposed that not only does light have the dual properties of waves and particles, but atoms and molecules do also. The wavelength of these particles is given by: λ=h/mv where m and v are the mass and velocity of the particle and h is Planck’s constant. The mathematical solution to the wave equation for electrons must satisfy three quantum conditions corresponding to three dimension of space. Each quantum condition introduces an integer, called a quantum number. The three principle quantum numbers are usually designated as follows: • n, principal quantum number, exclusively determines the energy orbital • l, angular momentum quantum number determines, the shape of the orbital • ml, magnetic quantum number, determines orientation of the orbital in space • ms, a fourth quantum number that takes into consideration the electron spin, electrons spin, clockwise and counter clockwise about the orbital in space. Quantization is not a difficult thing to understand because it exists in lots of every day examples. For example, money is not quantized, but coinage money is quantized and the minimum quantum coin in the US is a penny. The first quantum number says that electrons can only be in "special" orbits. All other orbits are just not possible. They could "jump" between these special orbits, however, and when they jumped they would wiggle a little bit, producing radiation. The radiation is characteristic of the wiggle between the energy levels. The Pauli exclusion principle states that no two electrons in an atom may have the same set of all four quantum numbers and helps set the conditions for the radiation (wiggle) between energy levels. Chemical Bonding Molecules are collections of atoms bound to each other that exist in the three phases. The electrons located in the outermost energy level of an atom play a major role in determining the atom’s chemical properties. These outermost electrons are called valence electrons. Thus the oxygen that we breathe is a molecule made up of two oxygen atoms combined and written as O2. Atoms can combine in several ways to form molecules. One way, is by sharing valence electrons to make a more stable compound. This type of grouping is called a covalent bond. This type of attraction can hold molecules together. Remember from Superman that diamond is the strongest material Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 4 of 8 known to man. The carbon atoms in diamond form covalent bonds. Another way of forming molecules is by transferring electrons between two atoms. One atom will gain an electron and the other atom will lose an electron. This type of bonding is called an ionic bond. Table salt, (sodium chloride NaCl) is an example of an ionic compound. Na + and Cl- ions are packed together in equal concentrations. The sum of the ionic charges in the formula is always zero. A different type of bonding exists in metals. In metals, all the atoms share all the electrons at one time. Thus metals easily conduct electricity because an extra electron can be added or removed without removing it from a single discrete atom. These materials are shiny, malleable and good conductors of heat and electricity. Most metals are on the left hand side of the periodic table. There are other types of bonding which are important in nanotechnology. Molecules and atoms can be drawn together by relatively weak forces collectively called van der Waals forces or interactions. These three forces are London forces sometimes called dispersive forces, dipole-dipole forces and hydrogen bonding. Nonpolar (non-charged) compounds do form solids, but at very low temperatures. Very weak attractions called dispersion forces occur when temporary dipoles form within nonpolar molecules. Remember that electrons in molecules are not always distributed symmetrically. For polar molecules, attractive forces called dipoledipole attraction occur between the positive end of one molecule and the negative end of another. These partial charges attract neighboring H-Cl molecules as shown in the diagram: dipoledipole forces are shown in green. The strength of these attractions increases with increasing polarity of the molecules. Hydrogen bonds occur between very specific types of atoms and molecules. In certain polar molecules, strong dipoles occur when a hydrogen atom is attached to an atom of fluorine, oxygen, or nitrogen, all of which have high electro-negativity values. Although these hydrogen bonds are weak, they can play an important role in the structure and behavior of matter, like water. These bonds also play an important role in at least two strands of DNA. Self-Assembly Molecular self-assembly is the assembly of molecules without guidance or management from an outside source. Self-assembly can occur spontaneously in nature, such as the self-assembly of the lipid bilayer membrane. The process of self-assembly in nature is governed by inter-molecular and intra-molecular forces that drive the molecules into a stable, low energy state. These forces were discussed earlier and include hydrogen bonding, electrostatic interactions, hydrophilic interactions and van der Waals forces. Self-assembly is thus referred to as a ‘bottom-up’ manufacturing technique, as compared to lithography being a ‘top-down’ technique (lithography is the method of creating small Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 5 of 8 structures from a large block of matter). There are two major approaches possible for molecular self-assembly. The two strategies are: electrostatic self-assembly (or layer-by-layer) and self-assembled monolayers (SAM). Electrostatic self-assembly involves alternate absorption of anionic (+) and catonic (-) electrolytes into suitable substrates. The latter strategy of self-assembled monolayers (SAMs) is based on thiols and silanes. Thiols are organic compounds that contain a functional group composed of a sulfur atom and a hydrogen atom (-SH). This functional group is referred to as either a thiol group or a sulfhydryl group. More traditionally, thiols are often referred to as mercaptans. Silane is a chemical compound with a chemical formula SiH4 (silicon and four hydrogen atoms). It is the silicon analogue of methane. Silanes consist of a chain of silicon atoms bound to hydrogen atoms. H Nanotechnology and Society How does society determine who, what, when, where, and how to use its technological knowledge and inventions? Nanotechnology is driven by the aim to advance broad societal goals. What are some of the practical implications and cultural context of nanotechnology research and development and how will these impact the US and the world? The world must be concerned about: • • • • environmental safety and health impact of nanotechnology. educational opportunities in this growing new field of science. broad impact on ethical and legal issues. who will own this technology. An excellent report exploring the potential societal impacts of nanotechnology has been edited by Mihail C. Roco and William S. Bainbridge of the National Science Foundation. Some Nanotechnology Products As of November 26, 2006 there are over 356 products or product lines that are based on nanotechnology. One of my favorite products is the new Samsung front-loading washer which uses Silver Ions in its wash and rinse cycles to kill 99.9% of tested bacteria to sanitize laundry, all in cold water without the use of bleach. Samsung developed a system to use Silver, widely known for its anti-microbial properties, in the wash water of its newest line of washing machines. Metallic silver atoms, electrolytically stripped of an electron, are injected during the wash and rinse cycles, allowing over 100 quadrillion silver ions to penetrate deep into the fabric to sanitize clothing without the need for hot water or bleach. Clarity Fog Eliminator by NanoFilm Ltd. is a coating that will protect and prevent fog on glass surfaces. NanoFilm's nanotechnology pursuits in optical lenses include self-assembled top coatings for non-reflective lenses to both seal and repel dirt, dust and skin oils from the fragile inorganic anti-reflective (AR) layers. Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 6 of 8 One of the oldest applications that employed nanotechnology was used by the cowboys when they would put a Silver Dollar in the bottom of their canteens. The silver prevented bacteria from growing in the water from the creek. References 1. National Nanotechnology Initiative, http://www.nano.gov/html/facts/whatIsNano.html 2. Nobel Prize interview: http//nobelprize.org/chemistry/laureates Additional Reading 1. Ted Sargent, “The Dance of the Molecules”, 2006. 2. George Whitesides and Bartosz Grzybowski, “Self-assembly at All Scales,” Science, 29 March 2002, vol. 295, pp2418-21. 3. Robert F. Service, “Nanotechnology Grows Up”, Science, vol. 304, 18 June 2004, pp 1732-34. 4. “Nanotechnology: Societal Implications—Maximizing Benefits for Humanity,” Edited by Mihail C. Roco and William S. Bainbridge of the National Science Foundation, December 2003. 5. Nanoproducts: http://www.nanotechproject.org/index.php?id=44 6. Mick Wilson, Kamali Kannangara, Geoff Smith, Michele Simmons and Burkhard Raguse, Nanotechnology-basic science and emerging technologies, 20004, Chapman & Hall/CRC. 7. Various Authors, “Understanding Nanotechnology”, Scientific American, 2002. 8. Learn more visit: www.nnin.org 9. For younger students: www.nanooze.org 10. Interdisciplinary Education Group: http://mrsec.wisc.edu/Edetc/index.html 11. The Search for DNA - The Birth of Molecular Biology: http://www.accessexcellence.org/RC/AB/BC/Search_for_DNA.html Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 7 of 8 12. DNA: The Instruction Manual for All Life: http://www.thetech.org/exhibits/online/genome/ Chapter 1: Atoms, Molecules and Molecular States Gary Harris & J.A. Griffin – Copyright March 2007 Page 8 of 8