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Topoisomer
Topoisomers or topological isomers are molecules with the same chemical formula and stereochemical bond connectivities but different topologies. Examples of molecules for which there exist topoisomers include DNA, which can form knots, and catenanes. Each topoisomer of a given DNA molecule possesses a different linking number associated with it. DNA topoisomers can be interchanged by enzymes called topoisomerases. Using a topoisomerase along with an intercalator, topoisomers with different linking number may be separated on an agarose gel via gel electrophoresis. See also * Mechanically-interlocked molecular architectures * Catenane * Rotaxanes * Molecular knot * 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 ... References * ''New Molecular Topolog ...
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Topoisomerase
DNA topoisomerases (or topoisomerases) are enzymes that catalyze changes in the topological state of DNA, interconverting relaxed and supercoiled forms, linked (catenated) and unlinked species, and knotted and unknotted DNA. Topological issues in DNA arise due to the intertwined nature of its double-helical structure, which, for example, can lead to overwinding of the DNA duplex during DNA replication and transcription. If left unchanged, this torsion would eventually stop the DNA or RNA polymerases involved in these processes from continuing along the DNA helix. A second topological challenge results from the linking or tangling of DNA during replication. Left unresolved, links between replicated DNA will impede cell division. The DNA topoisomerases prevent and correct these types of topological problems. They do this by binding to DNA and cutting the sugar-phosphate backbone of either one (type I topoisomerases) or both (type II topoisomerases) of the DNA strands. This transien ...
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Topology
In mathematics, topology (from the Greek language, Greek words , and ) is concerned with the properties of a mathematical object, geometric object that are preserved under Continuous function, continuous Deformation theory, deformations, such as Stretch factor, stretching, Twist (mathematics), twisting, crumpling, and bending; that is, without closing holes, opening holes, tearing, gluing, or passing through itself. A topological space is a set (mathematics), set endowed with a structure, called a ''Topology (structure), topology'', which allows defining continuous deformation of subspaces, and, more generally, all kinds of continuity (mathematics), continuity. Euclidean spaces, and, more generally, metric spaces are examples of a topological space, as any distance or metric defines a topology. The deformations that are considered in topology are homeomorphisms and homotopy, homotopies. A property that is invariant under such deformations is a topological property. Basic exampl ...
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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 biochemistry, the distinction from ions is dropped and ''molecule'' is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.g. water (two hydrogen atoms and one oxygen atom; H2O). In the kinetic theory of gases, the term ''molecule'' is often used for any gaseous particle regardless of its composition. This relaxes the requirement that a molecule contains two or more atoms, since the noble gases are individual atoms. Atoms and complexes connected by non-covalent interactions, such as hydrogen bonds or ionic bonds, are typically not consid ...
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Gel Electrophoresis
Gel electrophoresis is a method for separation and analysis of biomacromolecules ( DNA, RNA, proteins, etc.) and their fragments, based on their size and charge. It is used in clinical chemistry to separate proteins by charge or size (IEF agarose, essentially size independent) and in biochemistry and molecular biology to separate a mixed population of DNA and RNA fragments by length, to estimate the size of DNA and RNA fragments or to separate proteins by charge. Nucleic acid molecules are separated by applying an electric field to move the negatively charged molecules through a matrix of agarose or other substances. Shorter molecules move faster and migrate farther than longer ones because shorter molecules migrate more easily through the pores of the gel. This phenomenon is called sieving. Proteins are separated by the charge in agarose because the pores of the gel are too small to sieve proteins. Gel electrophoresis can also be used for the separation of nanoparticles. ...
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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 smallest examples of Borromean rings. The synthesis of molecular Borromean rings was reported in 2004 by the group of J. Fraser Stoddart. The so-called Borromeate is made up of three interpenetrated macrocycles formed through templated self assembly as complexes of zinc. The synthesis of the macrocyclic systems involves self-assembles of two organic building blocks: 2,6-diformylpyridine (an aromatic compound with two aldehyde groups positioned '' ortho'' to the nitrogen atom of the pyridine ring) and a symmetric diamine containing a ''meta''-substituted 2,2'-bipyridine group. Zinc acetate is added as the template for the reaction, resulting in one zinc cation in each of the six pentacoordinate complexation sites. Trifluoroacetic acid (TF ...
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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 naturally occurring knots are evolutionarily advantageous to nucleic acids or proteins, though knotting is thought to play a role in the structure, stability, and function of knotted biological molecules. The mechanism by which knots naturally form in molecules, and the mechanism by which a molecule is stabilized or improved by knotting, is ambiguous. The study of molecular knots involves the formation and applications of both naturally occurring and chemically synthesized molecular knots. Applying chemical topology and knot theory to molecular knots allows biologists to better understand the structures and synthesis of knotted organic molecules. The term ''knotane'' was coined by Vögtle ''et al.'' in 2000 to describe molecular knots by an ...
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Rotaxanes
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 trapped since the ends of the dumbbell (often called ''stoppers'') are larger than the internal diameter of the ring and prevent dissociation (unthreading) of the components since this would require significant distortion of the covalent bonds. Much of the research concerning rotaxanes and other mechanically interlocked molecular architectures, such as catenanes, has been focused on their efficient synthesis or their utilization as artificial molecular machines. However, examples of rotaxane substructure have been found in naturally occurring peptides, including: cystine knot peptides, cyclotides or lasso-peptides such as microcin J25. Synthesis The earliest reported synthesis of a rotaxane in 1967 relied on the statistical probability t ...
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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 separated without breaking the covalent bonds of the macrocycles. They are conceptually related to other mechanically interlocked molecular architectures, such as rotaxanes, molecular knots or molecular Borromean rings. Recently the terminology "mechanical bond" has been coined that describes the connection between the macrocycles of a catenane. Catenanes have been synthesised in two different ways: statistical synthesis and template-directed synthesis. Synthesis There are two primary approaches to the organic synthesis of catenanes. The first is to simply perform a ring-closing reaction with the hope that some of the rings will form around other rings giving the desired catenane product. This so-called "statistical approach" led to the fi ...
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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 to the keychain loop but they cannot be separated without breaking the loop. On the molecular level, the interlocked molecules cannot be separated without the breaking of the covalent bonds that comprise the conjoined molecules; this is referred to as a mechanical bond. Examples of mechanically interlocked molecular architectures include catenanes, rotaxanes, molecular knots, and molecular Borromean rings. Work in this area was recognized with the 2016 Nobel Prize in Chemistry to Bernard L. Feringa, Jean-Pierre Sauvage, and J. Fraser Stoddart. The synthesis of such entangled architectures has been made efficient by combining supramolecular chemistry with traditional covalent synthesis, however mechanically interlocked molecular architectu ...
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Intercalator
In chemistry, intercalation is the reversible inclusion or insertion of a molecule (or ion) into layered materials with layered structures. Examples are found in graphite and transition metal dichalcogenides. : Examples Graphite One famous intercalation host is graphite, which intercalates potassium as a guest. Intercalation expands the van der Waals gap between sheets, which requires energy. Usually this energy is supplied by charge transfer between the guest and the host solid, i.e., redox. Two potassium graphite compounds are KC8 and KC24. Carbon fluorides (e.g., (CF)x and (C4F)) are prepared by reaction of fluorine with graphitic carbon. The color is greyish, white, or yellow. The bond between the carbon and fluorine atoms is covalent, thus fluorine is not intercalated. Such materials have been considered as a cathode in various lithium batteries. Treating graphite with strong acids in the presence of oxidizing agents causes the graphite to oxidise. Graphite bisulfate, 24s ...
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Agarose
Agarose is a heteropolysaccharide, generally extracted from certain red seaweed. It is a linear polymer made up of the repeating unit of agarobiose, which is a disaccharide made up of D-galactose and 3,6-anhydro-L-galactopyranose. Agarose is one of the two principal components of agar, and is purified from agar by removing agar's other component, agaropectin. Agarose is frequently used in molecular biology for the separation of large molecules, especially DNA, by electrophoresis. Slabs of agarose gels (usually 0.7 - 2%) for electrophoresis are readily prepared by pouring the warm, liquid solution into a mold. A wide range of different agaroses of varying molecular weights and properties are commercially available for this purpose. Agarose may also be formed into beads and used in a number of chromatographic methods for protein purification. Structure Agarose is a linear polymer with a molecular weight of about 120,000, consisting of alternating D-galactose and 3,6-anhydro- ...
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