Supramolecular chemistry refers to the branch of
chemistry concerning
chemical systems composed of a
discrete number
In mathematics and statistics, a quantitative variable may be continuous or discrete if they are typically obtained by ''measuring'' or ''counting'', respectively. If it can take on two particular real values such that it can also take on all ...
of
molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...
s. The strength of the forces responsible for spatial organization of the system range from weak
intermolecular force
An intermolecular force (IMF) (or secondary force) is the force that mediates interaction between molecules, including the electromagnetic forces of attraction
or repulsion which act between atoms and other types of neighbouring particles, e.g. a ...
s,
electrostatic charge
Electric charge is the physical property of matter that causes charged matter to experience a force when placed in an electromagnetic field. Electric charge can be ''positive'' or ''negative'' (commonly carried by protons and electrons respecti ...
, or
hydrogen bond
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing ...
ing to strong
covalent bonding, provided that the electronic coupling strength remains small relative to the energy parameters of the component. While traditional chemistry concentrates on the covalent bond, supramolecular chemistry examines the weaker and reversible non-covalent interactions between molecules. These forces include hydrogen bonding,
metal coordination
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typical ...
,
hydrophobic forces,
van der Waals force
In molecular physics, the van der Waals force is a distance-dependent interaction between atoms or molecules. Unlike ionic or covalent bonds, these attractions do not result from a chemical electronic bond; they are comparatively weak and t ...
s,
pi–pi interaction
In chemistry, pi stacking (also called π–π stacking) refers to the presumptive attractive, noncovalent pi interactions (orbital overlap) between the pi bonds of aromatic rings. However this is a misleading description of the phenomena since ...
s and
electrostatic
Electrostatics is a branch of physics that studies electric charges at rest (static electricity).
Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word for am ...
effects.
Important concepts advanced by supramolecular chemistry include
molecular self-assembly
In chemistry and materials science, molecular self-assembly is the process by which molecules adopt a defined arrangement without guidance or management from an outside source. There are two types of self-assembly: intramolecular and intermo ...
,
molecular folding,
molecular recognition
The term molecular recognition refers to the specific interaction between two or more molecules through noncovalent bonding such as hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, π-π interactions, halogen ...
,
host–guest chemistry In supramolecular chemistry, host–guest chemistry describes inclusion compound, complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full covalent bond ...
,
mechanically-interlocked molecular architectures
In chemistry, mechanically-interlocked molecular architectures (MIMAs) are molecules that are connected as a consequence of their topology. This connection of molecules is analogous to keys on a keychain loop. The keys are not directly connected ...
, and
dynamic covalent chemistry
Dynamic covalent chemistry (DCvC) is a synthetic strategy employed by chemists to make complex supramolecular assemblies from discrete molecular building blocks. DCvC has allowed access to complex assemblies such as covalent organic frameworks, ...
. The study of
non-covalent interaction
In chemistry, a non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The ...
s is crucial to understanding many biological processes that rely on these forces for structure and function.
Biological systems
A biological system is a complex network which connects several biologically relevant entities. Biological organization spans several scales and are determined based different structures depending on what the system is. Examples of biological syst ...
are often the inspiration for supramolecular research.
Gallery
file:Supramolecular Assembly Lehn.jpg , Self-assembly of a circular double helicate
Cucurbituril gyroscope AngewChemIntEd 2002 v41 p275 hires.png, Host–guest complex within another host (cucurbituril
In host-guest chemistry, cucurbiturils are macrocyclic molecules made of glycoluril () monomers linked by methylene bridges (). The oxygen atoms are located along the edges of the band and are tilted inwards, forming a partly enclosed cavity ( ...
)
Rotaxane Crystal Structure EurJOrgChem page2565 year1998.png, Mechanically-interlocked molecules (rotaxane
In chemistry, a rotaxane () is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). The two components of a rotaxane are kinetically ...
)
Host Guest Complex Porphyrin Sanders AngewChemIntEdEngl 1995 1096.jpg, An example of a host–guest chemistry In supramolecular chemistry, host–guest chemistry describes inclusion compound, complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full covalent bond ...
Cucurbit-6-uril ActaCrystallB-Stru 1984 382.jpg, Host–guest complex with a p-xylylenediammonium bound within a cucurbituril
In host-guest chemistry, cucurbiturils are macrocyclic molecules made of glycoluril () monomers linked by methylene bridges (). The oxygen atoms are located along the edges of the band and are tilted inwards, forming a partly enclosed cavity ( ...
Lehn Beautiful Foldamer HelvChimActa 1598 2003.jpg, Intramolecular self-assembly
Self-assembly is a process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. When the ...
of a foldamer
In chemistry, a foldamer is a discrete chain molecule (oligomer) that folds into a conformationally ordered state in solution. They are artificial molecules that mimic the ability of proteins, nucleic acids, and polysaccharides to fold into ...
Silsesquioxane 3D interpenetrated network Dalton Transactions 2016 12312.png, 3D interpenetrated network in the crystal structure of silsesquioxane
History
The existence of intermolecular forces was first postulated by
Johannes Diderik van der Waals
Johannes Diderik van der Waals (; 23 November 1837 – 8 March 1923) was a Dutch theoretical physicist and thermodynamicist famous for his pioneering work on the equation of state for gases and liquids. Van der Waals started his career as a s ...
in 1873. However, Nobel laureate
Hermann Emil Fischer
Hermann Emil Louis Fischer (; 9 October 1852 – 15 July 1919) was a German chemist and 1902 recipient of the Nobel Prize in Chemistry. He discovered the Fischer esterification. He also developed the Fischer projection, a symbolic way of dra ...
developed supramolecular chemistry's philosophical roots. In 1894, Fischer suggested that
enzyme–substrate interactions take the form of a "lock and key", the fundamental principles of
molecular recognition
The term molecular recognition refers to the specific interaction between two or more molecules through noncovalent bonding such as hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, π-π interactions, halogen ...
and
host–guest chemistry In supramolecular chemistry, host–guest chemistry describes inclusion compound, complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full covalent bond ...
. In the early twentieth century non-covalent bonds were understood in gradually more detail, with the hydrogen bond being described by
Latimer Latimer may refer to:
Places England
* Latimer, Buckinghamshire, a village
** Latimer and Ley Hill, a civil parish that until 2013 was just called "Latimer"
* Latimer, Leicester, an electoral ward and administrative division of the city of Leices ...
and Rodebush in 1920.
The use of these principles led to an increasing understanding of
protein structure
Protein structure is the molecular geometry, three-dimensional arrangement of atoms in an amino acid-chain molecule. Proteins are polymers specifically polypeptides formed from sequences of amino acids, the monomers of the polymer. A single ami ...
and other biological processes. For instance, the important breakthrough that allowed the elucidation of the
double helical structure of
DNA occurred when it was realized that there are two separate strands of nucleotides connected through hydrogen bonds. The use of non-covalent bonds is essential to replication because they allow the strands to be separated and used to template new double stranded DNA. Concomitantly, chemists began to recognize and study synthetic structures based on non-covalent interactions, such as
micelle
A micelle () or micella () (plural micelles or micellae, respectively) is an aggregate (or supramolecular assembly) of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension (also known as associated col ...
s and
microemulsion Microemulsions are clear, thermodynamically stable isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be ...
s.
Eventually, chemists were able to take these concepts and apply them to synthetic systems. The breakthrough came in the 1960s with the synthesis of the
crown ether
In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . I ...
s by
Charles J. Pedersen
Charles John Pedersen ( ja, 安井 良男, ''Yasui Yoshio'', October 3, 1904 – October 26, 1989) was an American organic chemist best known for describing methods of synthesizing crown ethers during his entire 42-year career as a chemist for D ...
. Following this work, other researchers such as
Donald J. Cram
Donald James Cram (April 22, 1919 – June 17, 2001) was an American chemist who shared the 1987 Nobel Prize in Chemistry with Jean-Marie Lehn and Charles J. Pedersen "for their development and use of molecules with structure-specific inte ...
,
Jean-Marie Lehn
Jean-Marie Lehn (born 30 September 1939) is a French chemist. He received the Nobel Prize in Chemistry together with Donald Cram and Charles Pedersen in 1987 for his synthesis of cryptands. Lehn was an early innovator in the field of supramole ...
and
Fritz Vögtle
Fritz originated as a German nickname for Friedrich, or Frederick (''Der Alte Fritz'', and ''Stary Fryc'' were common nicknames for King Frederick II of Prussia and Frederick III, German Emperor) as well as for similar names including Fridolin a ...
became active in synthesizing shape- and ion-selective receptors, and throughout the 1980s research in the area gathered a rapid pace with concepts such as mechanically interlocked molecular architectures emerging.
The importance of supramolecular chemistry was established by the 1987
Nobel Prize
The Nobel Prizes ( ; sv, Nobelpriset ; no, Nobelprisen ) are five separate prizes that, according to Alfred Nobel's will of 1895, are awarded to "those who, during the preceding year, have conferred the greatest benefit to humankind." Alfre ...
for Chemistry which was awarded to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen in recognition of their work in this area. The development of selective "host–guest" complexes in particular, in which a host molecule recognizes and selectively binds a certain guest, was cited as an important contribution.
In the 1990s, supramolecular chemistry became even more sophisticated, with researchers such as
James Fraser Stoddart
Sir James Fraser Stoddart (born 24 May 1942) is a British-American chemist who is Board of Trustees Professor of Chemistry and head of the Stoddart Mechanostereochemistry Group in the Department of Chemistry at Northwestern University in ...
developing
molecular machinery and highly complex
self-assembled
Self-assembly is a process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. When the ...
structures, and
Itamar Willner
Itamar Willner FRSC is an Israeli chemist who has been a professor at the Hebrew University of Jerusalem since 1986.
He completed his PhD in physical organic chemistry at the Hebrew University of Jerusalem in 1978.
He was awarded the Israel P ...
developing sensors and methods of electronic and biological interfacing. During this period,
electrochemical
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outco ...
and
photochemical
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100 to 400 nm), visible light (400– ...
motifs became integrated into supramolecular systems in order to increase functionality, research into synthetic self-replicating system began, and work on molecular information processing devices began. The emerging science of
nanotechnology
Nanotechnology, also shortened to nanotech, is the use of matter on an atomic, molecular, and supramolecular scale for industrial purposes. The earliest, widespread description of nanotechnology referred to the particular technological goal o ...
also had a strong influence on the subject, with building blocks such as
fullerene
A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecule may be a hollow sphere, ...
s,
nanoparticle
A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 10 ...
s, and
dendrimer
Dendrimers are highly ordered, branched polymeric molecules. Synonymous terms for dendrimer include arborols and cascade molecules. Typically, dendrimers are symmetric about the core, and often adopt a spherical three-dimensional morphology. The ...
s becoming involved in synthetic systems.
Control
Thermodynamics
Supramolecular complexes are formed by non-covalent interactions between two chemical moieties, which can be described as an host and a guest. Most commonly, the interacting species are held together by
hydrogen bond
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing ...
s. The definition excludes compounds formed by electrostatic interactions, which are called
ion pair
In chemistry, ion association is a chemical reaction whereby ions of opposite electric charge come together in solution to form a distinct chemical entity. Ion associates are classified, according to the number of ions that associate with each ...
s.
In solution, the host H, guest G, and complexes H
pG
q, will be in equilibrium with each other. In the simplest case, p=q=1, the equilibrium can be written as
:
The value of the
equilibrium constant
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency ...
, K, for this reaction can, in principle, be
determined
Determinacy is a subfield of set theory, a branch of mathematics, that examines the conditions under which one or the other player of a game has a winning strategy, and the consequences of the existence of such strategies. Alternatively and simil ...
by any of the techniques described below. Some examples are shown in the following table.
[
:
The ]Gibbs free energy
In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work (physics), work that may be performed by a closed system, thermodynamically closed system a ...
change, , for this reaction is the sum of an enthalpy term, and an entropy term .
:
Both and values can be determined at a given temperature, , by means of Isothermal titration calorimetry
Isothermal titration calorimetry (ITC) is a physical technique used to determine the thermodynamic parameters of interactions in solution. It is most often used to study the binding of small molecules (such as medicinal compounds) to larger macro ...
. For an example, see Sessler. ''et.al.'' In that example a macrocyclic ring with 4 protonated nitrogen atoms encapsulates a chloride anion; illustrations of ITC data and a titration curve are reproduced in Steed&Atwood. (pp 15–16) The value of the equilibrium constant and the stoichiometry of the species formed were found to be strongly solvent-dependent. With nitromethane solutions values of ΔH = 8.55 kJmol−1 and ΔS = -9.1 JK−1mol−1 were obtained.
Environment
The molecular environment around a supramolecular system is also of prime importance to its operation and stability. Many solvents
A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
have strong hydrogen bonding, electrostatic, and charge-transfer capabilities, and are therefore able to become involved in complex equilibria with the system, even breaking complexes completely. For this reason, the choice of solvent can be critical.
Concepts
Molecular self-assembly
Molecular self-assembly
In chemistry and materials science, molecular self-assembly is the process by which molecules adopt a defined arrangement without guidance or management from an outside source. There are two types of self-assembly: intramolecular and intermo ...
is the construction of systems without guidance or management from an outside source (other than to provide a suitable environment). The molecules are directed to assemble through non-covalent interactions. Self-assembly may be subdivided into intermolecular self-assembly (to form a supramolecular assembly
In chemistry, a supramolecular assembly is a complex of molecules held together by noncovalent bonds. While a supramolecular assembly can be simply composed of two molecules (e.g., a DNA double helix or an inclusion compound), or a defined nu ...
), and intramolecular self-assembly (or folding
Fold, folding or foldable may refer to:
Arts, entertainment, and media
* ''Fold'' (album), the debut release by Australian rock band Epicure
* Fold (poker), in the game of poker, to discard one's hand and forfeit interest in the current pot
*Abov ...
as demonstrated by foldamers
In chemistry, a foldamer is a discrete chain molecule (oligomer) that folds into a conformationally ordered state in solution. They are artificial molecules that mimic the ability of proteins, nucleic acids, and polysaccharides to fold into ...
and polypeptides). Molecular self-assembly also allows the construction of larger structures such as micelles
A micelle () or micella () (plural micelles or micellae, respectively) is an aggregate (or supramolecular assembly) of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension (also known as associated colloi ...
, membranes
A membrane is a selective barrier; it allows some things to pass through but stops others. Such things may be molecules, ions, or other small particles. Membranes can be generally classified into synthetic membranes and biological membranes. Bi ...
, vesicles
Vesicle may refer to:
; In cellular biology or chemistry
* Vesicle (biology and chemistry), a supramolecular assembly of lipid molecules, like a cell membrane
* Synaptic vesicle
; In human embryology
* Vesicle (embryology), bulge-like feature ...
, liquid crystals
Liquid crystal (LC) is a state of matter whose properties are between those of conventional liquids and those of solid crystals. For example, a liquid crystal may flow like a liquid, but its molecules may be oriented in a crystal-like way. The ...
, and is important to crystal engineering Crystal engineering studies the design and synthesis of solid-state structures with desired properties through deliberate control of intermolecular interactions. It is an interdisciplinary academic field, bridging solid-state and supramolecular ch ...
.[ ]
Molecular recognition and complexation
Molecular recognition
The term molecular recognition refers to the specific interaction between two or more molecules through noncovalent bonding such as hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, π-π interactions, halogen ...
is the specific binding of a guest molecule to a complementary host molecule to form a host–guest complex. Often, the definition of which species is the "host" and which is the "guest" is arbitrary. The molecules are able to identify each other using non-covalent interactions. Key applications of this field are the construction of molecular sensor
A molecular sensor or chemosensor is a molecular structure (organic or inorganic complexes) that is used for sensing of an analyte to produce a detectable change or a signal. The action of a chemosensor, relies on an interaction occurring at the mo ...
s and catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycl ...
.
Template-directed synthesis
Molecular recognition and self-assembly may be used with reactive species in order to pre-organize a system for a chemical reaction (to form one or more covalent bonds). It may be considered a special case of supramolecular catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycl ...
. Non-covalent bonds between the reactants and a "template" hold the reactive sites of the reactants close together, facilitating the desired chemistry. This technique is particularly useful for situations where the desired reaction conformation is thermodynamically or kinetically unlikely, such as in the preparation of large macrocycles. This pre-organization also serves purposes such as minimizing side reactions, lowering the activation energy
In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules p ...
of the reaction, and producing desired stereochemistry
Stereochemistry, a subdiscipline of chemistry, involves the study of the relative spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereo ...
. After the reaction has taken place, the template may remain in place, be forcibly removed, or may be "automatically" decomplexed on account of the different recognition properties of the reaction product. The template may be as simple as a single metal ion or may be extremely complex.
Mechanically interlocked molecular architectures
Mechanically interlocked molecular architectures
In chemistry, mechanically-interlocked molecular architectures (MIMAs) are molecules that are connected as a consequence of their topology. This connection of molecules is analogous to keys on a keychain loop. The keys are not directly connected ...
consist of molecules that are linked only as a consequence of their topology. Some non-covalent interactions may exist between the different components (often those that were utilized in the construction of the system), but covalent bonds do not. Supramolecular chemistry, and template-directed synthesis in particular, is key to the efficient synthesis of the compounds. Examples of mechanically interlocked molecular architectures include catenane
In macromolecular chemistry, a catenane () is a mechanically interlocked molecular architecture consisting of two or more interlocked macrocycles, i.e. a molecule containing two or more intertwined rings. The interlocked rings cannot be se ...
s, rotaxane
In chemistry, a rotaxane () is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). The two components of a rotaxane are kinetically ...
s, molecular knot
In chemistry, a molecular knot is a mechanically interlocked molecular architecture that is analogous to a macroscopic knot. Naturally-forming molecular knots are found in organic molecules like DNA, RNA, and proteins. It is not certain that nat ...
s, molecular Borromean rings
In chemistry, molecular Borromean rings are an example of a mechanically-interlocked molecular architecture in which three macrocycles are interlocked in such a way that breaking any macrocycle allows the others to dissociate. They are the smal ...
and ravels.
Dynamic covalent chemistry
In dynamic covalent chemistry
Dynamic covalent chemistry (DCvC) is a synthetic strategy employed by chemists to make complex supramolecular assemblies from discrete molecular building blocks. DCvC has allowed access to complex assemblies such as covalent organic frameworks, ...
covalent bonds are broken and formed in a reversible reaction under thermodynamic control. While covalent bonds are key to the process, the system is directed by non-covalent forces to form the lowest energy structures.
Biomimetics
Many synthetic supramolecular systems are designed to copy functions of biological systems. These biomimetic
Biomimetics or biomimicry is the emulation of the models, systems, and elements of nature for the purpose of solving complex human problems. The terms "biomimetics" and "biomimicry" are derived from grc, βίος (''bios''), life, and μίμησ ...
architectures can be used to learn about both the biological model and the synthetic implementation. Examples include photoelectrochemical systems, catalytic systems, protein design
Protein design is the rational design of new protein molecules to design novel activity, behavior, or purpose, and to advance basic understanding of protein function. Proteins can be designed from scratch (''de novo'' design) or by making calcul ...
and self-replication
Self-replication is any behavior of a dynamical system that yields construction of an identical or similar copy of itself. Biological cells, given suitable environments, reproduce by cell division. During cell division, DNA is replicated and c ...
.
Imprinting
Molecular imprinting
Molecular imprinting is a technique to create template-shaped cavities in polymer matrices with predetermined selectivity and high affinity. This technique is based on the system used by enzymes for substrate recognition, which is called the "loc ...
describes a process by which a host is constructed from small molecules using a suitable molecular species as a template. After construction, the template is removed leaving only the host. The template for host construction may be subtly different from the guest that the finished host binds to. In its simplest form, imprinting utilizes only steric
Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions ...
interactions, but more complex systems also incorporate hydrogen bonding and other interactions to improve binding strength and specificity.
Molecular machinery
Molecular machine
A molecular machine, nanite, or nanomachine is a molecular component that produces quasi-mechanical movements (output) in response to specific stimuli (input). In cellular biology, macromolecular machines frequently perform tasks essential for ...
s are molecules or molecular assemblies that can perform functions such as linear or rotational movement, switching, and entrapment. These devices exist at the boundary between supramolecular chemistry and nanotechnology
Nanotechnology, also shortened to nanotech, is the use of matter on an atomic, molecular, and supramolecular scale for industrial purposes. The earliest, widespread description of nanotechnology referred to the particular technological goal o ...
, and prototypes have been demonstrated using supramolecular concepts. Jean-Pierre Sauvage
Jean-Pierre Sauvage (; born 21 October 1944) is a French coordination chemist working at Strasbourg University. He graduated from the National School of Chemistry of Strasbourg (now known as ECPM Strasbourg), in 1967. He has specialized in s ...
, Sir J. Fraser Stoddart and Bernard L. Feringa
Bernard Lucas Feringa (, born 18 May 1951) is a Dutch synthetic organic chemist, specializing in molecular nanotechnology and homogeneous catalysis. He is the Jacobus van 't Hoff Distinguished Professor of Molecular Sciences, at the Stratingh ...
shared the 2016 Nobel Prize in Chemistry
)
, image = Nobel Prize.png
, alt = A golden medallion with an embossed image of a bearded man facing left in profile. To the left of the man is the text "ALFR•" then "NOBEL", and on the right, the text (smaller) "NAT•" then "M ...
for the 'design and synthesis of molecular machines'.
Building blocks
Supramolecular systems are rarely designed from first principles. Rather, chemists have a range of well-studied structural and functional building blocks that they are able to use to build up larger functional architectures. Many of these exist as whole families of similar units, from which the analog with the exact desired properties can be chosen.
Synthetic recognition motifs
*The pi-pi charge-transfer interactions of bipyridinium with dioxyarenes or diaminoarenes have been used extensively for the construction of mechanically interlocked systems and in crystal engineering Crystal engineering studies the design and synthesis of solid-state structures with desired properties through deliberate control of intermolecular interactions. It is an interdisciplinary academic field, bridging solid-state and supramolecular ch ...
.
*The use of crown ether
In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . I ...
binding with metal or ammonium cations is ubiquitous in supramolecular chemistry.
*The formation of carboxylic acid
In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxyl ...
dimers and other simple hydrogen bonding interactions.
*The complexation
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
of bipyridine Bipyridines also known as bipyridyls, dipyridyls, and dipyridines, are a family of chemical compounds with the formula (C5H4N)2, consisting of two pyridyl (C5H4N) rings. Pyridine is an aromatic nitrogen-containing heterocycle. Bipyridines are of si ...
s or terpyridine
Terpyridine (2,2';6',2"-terpyridine, often abbreviated to Terpy or Tpy) is a heterocyclic compound derived from pyridine. It is a white solid that is soluble in most organic solvents. The compound is mainly used as a ligand in coordination chemis ...
s with ruthenium
Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemic ...
, silver
Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
or other metal ions
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
is of great utility in the construction of complex architectures of many individual molecules.
*The complexation of porphyrin
Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical ...
s or phthalocyanine
Phthalocyanine () is a large, aromatic, macrocyclic, organic compound with the formula and is of theoretical or specialized interest in chemical dyes and photoelectricity.
It is composed of four isoindole units linked by a ring of nitrogen atom ...
s around metal ions gives access to catalytic, photochemical
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100 to 400 nm), visible light (400– ...
and electrochemical
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outco ...
properties in addition to the complexation itself. These units are used a great deal by nature.
Macrocycles
Macrocycles
Macrocycles are often described as molecules and ions containing a ring of twelve or more atoms. Classical examples include the crown ethers, calixarenes, porphyrins, and cyclodextrins. Macrocycles describe a large, mature area of chemistry.
...
are very useful in supramolecular chemistry, as they provide whole cavities that can completely surround guest molecules and may be chemically modified to fine-tune their properties.
*Cyclodextrin
Cyclodextrins are a family of cyclic oligosaccharides, consisting of a macrocyclic ring of glucose subunits joined by α-1,4 glycosidic bonds. Cyclodextrins are produced from starch by enzymatic conversion. They are used in food, pharmaceutica ...
s, calixarene
A calixarene is a macrocycle or cyclic oligomer based on a methylene-linked phenols. With hydrophobic cavities that can hold smaller molecules or ions, calixarenes belong to the class of cavitands known in host–guest chemistry.
Nomenclature
C ...
s, cucurbituril
In host-guest chemistry, cucurbiturils are macrocyclic molecules made of glycoluril () monomers linked by methylene bridges (). The oxygen atoms are located along the edges of the band and are tilted inwards, forming a partly enclosed cavity ( ...
s and crown ether
In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . I ...
s are readily synthesized in large quantities, and are therefore convenient for use in supramolecular systems.
*More complex cyclophane
In organic chemistry, a cyclophane is a hydrocarbon consisting of an aromatic unit (typically a benzene ring) and a chain that forms a bridge between two non-adjacent positions of the aromatic ring. More complex derivatives with multiple aromatic ...
s, and cryptand
In chemistry, cryptands are a family of synthetic, bicyclic and polycyclic, multidentate ligands for a variety of cations. The Nobel Prize for Chemistry in 1987 was given to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen for th ...
s can be synthesised to provide more tailored recognition properties.
*Supramolecular metallocycles are macrocyclic aggregates with metal ions in the ring, often formed from angular and linear modules. Common metallocycle shapes in these types of applications include triangles, squares, and pentagons, each bearing functional group
In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the res ...
s that connect the pieces via "self-assembly."
*Metallacrown
image:Mcwiki.png, 300px, Figure showing the metallacrown analogy to the organic crown ether. Ligand substituents are omitted for clarity.a) 12-crown-4 b) 12-MCFe(III)N(shi)-4c) 15-crown-5 d) 15-MCCu(II)N(picHA)-5
In chemistry, metallacrowns are a ...
s are metallomacrocycles generated via a similar self-assembly
Self-assembly is a process in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. When the ...
approach from fused chelate-rings.
Structural units
Many supramolecular systems require their components to have suitable spacing and conformations relative to each other, and therefore easily employed structural units are required.
*Commonly used spacers and connecting groups include polyether
In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be ...
chains, biphenyls and triphenyl
Terphenyls are a group of closely related aromatic hydrocarbons. Also known as diphenylbenzenes or triphenyls, they consist of a central benzene ring substituted with two phenyl groups. There are three substitution patterns: ''ortho''-terphenyl ...
s, and simple alkyl chain
In organic chemistry, an alkyl group is an alkane missing one hydrogen.
The term ''alkyl'' is intentionally unspecific to include many possible substitutions.
An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...
s. The chemistry for creating and connecting these units is very well understood.
*nanoparticles
A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 10 ...
, nanorods
In nanotechnology, nanorods are one morphology of nanoscale objects. Each of their dimensions range from 1–100 nm. They may be synthesized from metals or semiconducting materials. Standard aspect ratios (length divided by width) are 3-5. Na ...
, fullerenes
A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecule may be a hollow sphere, ...
and dendrimers
Dendrimers are highly ordered, branched polymeric molecules. Synonymous terms for dendrimer include arborols and cascade molecules. Typically, dendrimers are symmetric about the core, and often adopt a spherical three-dimensional morphology. The ...
offer nanometer-sized structure and encapsulation units.
*Surfaces
A surface, as the term is most generally used, is the outermost or uppermost layer of a physical object or space.
Surface or surfaces may also refer to:
Mathematics
*Surface (mathematics), a generalization of a plane which needs not be flat
* Su ...
can be used as scaffolds for the construction of complex systems and also for interfacing electrochemical systems with electrodes
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials dep ...
. Regular surfaces can be used for the construction of self-assembled monolayer
Self-assembled monolayers (SAM) of organic molecules are molecular assemblies formed spontaneously on surfaces by adsorption and are organized into more or less large ordered domains. In some cases molecules that form the monolayer do not interact ...
s and multilayer
In the physical sciences, a multilayer or stratified medium is a stack of different thin films. Typically, a multilayer is man made for a specific purpose. Since layers are thin with respect to some relevant length scale, interface effects are m ...
s.
* The understanding of intermolecular interactions in solids has undergone a major renaissance via inputs from different experimental and computational methods in the last decade. This includes high-pressure studies in solids and "in situ" crystallization of compounds which are liquids at room temperature along with the utilization of electron density analysis, crystal structure prediction and DFT calculations in solid state to enable a quantitative understanding of the nature, energetics and topological properties associated with such interactions in crystals.
Photo-chemically and electro-chemically active units
*Porphyrin
Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical ...
s, and phthalocyanine
Phthalocyanine () is a large, aromatic, macrocyclic, organic compound with the formula and is of theoretical or specialized interest in chemical dyes and photoelectricity.
It is composed of four isoindole units linked by a ring of nitrogen atom ...
s have highly tunable photochemical and electrochemical activity as well as the potential to form complexes.
*Photochromic
Photochromism is the reversible transformation of a chemical species (photoswitch) between two forms by the absorption of electromagnetic radiation (photoisomerization), where the two forms have different absorption spectra. In plain language, th ...
and photoisomerizable groups can change their shapes and properties, including binding properties, upon exposure to light.
*Tetrathiafulvalene
Tetrathiafulvalene is an organosulfur compound with the formula (. Studies on this heterocyclic compound contributed to the development of molecular electronics. TTF is related to the hydrocarbon fulvalene, , by replacement of four CH groups ...
(TTF) and quinone
The quinones are a class of organic compounds that are formally "derived from aromatic compounds benzene.html" ;"title="uch as benzene">uch as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with ...
s have multiple stable oxidation state
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. ...
s, and therefore can be used in redox reactions
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a de ...
and electrochemistry.
*Other units, such as benzidine
Benzidine (trivial name), also called 1,1'- biphenyl-4,4'-diamine ( systematic name), is an organic compound with the formula (C6H4NH2)2. It is an aromatic amine. It is a component of a test for cyanide. Related derivatives are used in the pr ...
derivatives, viologen
Viologens are organic compounds with the formula (C5H4NR)2n+. In some viologens, the pyridyl groups are further modified.
Viologens are called so, because these compounds produce violet color on reduction iolet + Latin ''gen'', generator of ...
s, and fullerene
A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecule may be a hollow sphere, ...
s, are useful in supramolecular electrochemical devices.
Biologically-derived units
*The extremely strong complexation
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
between avidin
Avidin is a tetrameric biotin-binding protein produced in the oviducts of birds, reptiles and amphibians and deposited in the whites of their eggs. Dimeric members of the avidin family are also found in some bacteria. In chicken egg white, a ...
and biotin is instrumental in blood clotting
Coagulation, also known as clotting, is the process by which blood changes from a liquid to a gel, forming a blood clot. It potentially results in hemostasis, the cessation of blood loss from a damaged vessel, followed by repair. The mechanism ...
, and has been used as the recognition motif to construct synthetic systems.
*The binding of enzymes with their cofactors
Cofactor may also refer to:
* Cofactor (biochemistry), a substance that needs to be present in addition to an enzyme for a certain reaction to be catalysed
* A domain parameter in elliptic curve cryptography, defined as the ratio between the orde ...
has been used as a route to produce modified enzymes, electrically contacted enzymes, and even photoswitchable enzymes.
* DNA has been used both as a structural and as a functional unit in synthetic supramolecular systems.
Applications
Materials technology
Supramolecular chemistry has found many applications, in particular molecular self-assembly
In chemistry and materials science, molecular self-assembly is the process by which molecules adopt a defined arrangement without guidance or management from an outside source. There are two types of self-assembly: intramolecular and intermo ...
processes have been applied to the development of new materials. Large structures can be readily accessed using bottom-up synthesis as they are composed of small molecules requiring fewer steps to synthesize. Thus most of the bottom-up approaches to nanotechnology
Nanotechnology, also shortened to nanotech, is the use of matter on an atomic, molecular, and supramolecular scale for industrial purposes. The earliest, widespread description of nanotechnology referred to the particular technological goal o ...
are based on supramolecular chemistry. Many smart material
Smart materials, also called intelligent or responsive materials, are designed materials that have one or more properties that can be significantly changed in a controlled fashion by external stimuli, such as stress (physics), stress, moisture, ele ...
s are based on molecular recognition.
Catalysis
A major application of supramolecular chemistry is the design and understanding of catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s and catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycl ...
. Non-covalent interactions are extremely important in catalysis, binding reactants into conformations suitable for reaction and lowering the transition state
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked ...
energy of reaction. Template-directed synthesis is a special case of supramolecular catalysis. Encapsulation systems such as micelles
A micelle () or micella () (plural micelles or micellae, respectively) is an aggregate (or supramolecular assembly) of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension (also known as associated colloi ...
, dendrimers
Dendrimers are highly ordered, branched polymeric molecules. Synonymous terms for dendrimer include arborols and cascade molecules. Typically, dendrimers are symmetric about the core, and often adopt a spherical three-dimensional morphology. The ...
, and cavitand
In chemistry, a cavitand is a container-shaped molecule. The cavity of the cavitand allows it to engage in host–guest chemistry with guest molecules of a complementary shape and size. The original definition proposed by Cram includes many c ...
s are also used in catalysis to create microenvironments suitable for reactions (or steps in reactions) to progress that is not possible to use on a macroscopic scale.
Medicine
Design based on supramolecular chemistry has led to numerous applications in the creation of functional biomaterials and therapeutics. Supramolecular biomaterials afford a number of modular and generalizable platforms with tunable mechanical, chemical and biological properties. These include systems based on supramolecular assembly of peptides, host–guest macrocycles, high-affinity hydrogen bonding, and metal–ligand interactions.
A supramolecular approach has been used extensively to create artificial ion channels for the transport of sodium and potassium ions into and out of cells.
Supramolecular chemistry is also important to the development of new pharmaceutical therapies by understanding the interactions at a drug binding site. The area of drug delivery
Drug delivery refers to approaches, formulations, manufacturing techniques, storage systems, and technologies involved in transporting a pharmaceutical compound to its target site to achieve a desired therapeutic effect. Principles related to dr ...
has also made critical advances as a result of supramolecular chemistry providing encapsulation and targeted release mechanisms. In addition, supramolecular systems have been designed to disrupt protein–protein interaction
Protein–protein interactions (PPIs) are physical contacts of high specificity established between two or more protein molecules as a result of biochemical events steered by interactions that include electrostatic forces, hydrogen bonding and th ...
s that are important to cellular function.
Data storage and processing
Supramolecular chemistry has been used to demonstrate computation functions on a molecular scale. In many cases, photonic or chemical signals have been used in these components, but electrical interfacing of these units has also been shown by supramolecular signal transduction
Signal transduction is the process by which a chemical or physical signal is transmitted through a cell as a series of molecular events, most commonly protein phosphorylation catalyzed by protein kinases, which ultimately results in a cellular ...
devices. Data storage
Data storage is the recording (storing) of information (data) in a storage medium. Handwriting, phonographic recording, magnetic tape, and optical discs are all examples of storage media. Biological molecules such as RNA and DNA are cons ...
has been accomplished by the use of molecular switch
A molecular switch is a molecule that can be reversibly shifted between two or more stable states. The molecules may be shifted between the states in response to environmental stimuli, such as changes in pH, light, temperature, an electric curren ...
es with photochromic
Photochromism is the reversible transformation of a chemical species (photoswitch) between two forms by the absorption of electromagnetic radiation (photoisomerization), where the two forms have different absorption spectra. In plain language, th ...
and photoisomerizable units, by electrochromic
Electrochromism is a phenomenon in which a material displays changes in color or opacity in response to an electrical stimulus.
In this way, a smart window made of an electrochromic material can block specific wavelengths of ultraviolet, visib ...
and redox
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
-switchable units, and even by molecular motion. Synthetic molecular logic gate
A molecular logic gate is a molecule that performs a logical operation based on one or more physical or chemical inputs and a single output. The field has advanced from simple logic systems based on a single chemical or physical input to molecules ...
s have been demonstrated on a conceptual level. Even full-scale computations have been achieved by semi-synthetic DNA computer
DNA computing is an emerging branch of unconventional computing which uses DNA, biochemistry, and molecular biology hardware, instead of the traditional electronic computing. Research and development in this area concerns theory, experiments, a ...
s.
See also
* Organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clay ...
* Nanotechnology
Nanotechnology, also shortened to nanotech, is the use of matter on an atomic, molecular, and supramolecular scale for industrial purposes. The earliest, widespread description of nanotechnology referred to the particular technological goal o ...
References
External links
2D and 3D Models of Dodecahedrane and Cuneane Assemblies
an
– Thematic Series in the Open Access Beilstein Journal of Organic Chemistry
{{BranchesofChemistry
Chemistry