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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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Catenane Crystal Structure ChemComm Page634 1991 Commons
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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Catenane ChemComm 244 1985
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 ...
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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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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 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 probabili ...
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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 current, microenvironment, or in the presence of ions and other ligands. In some cases, a combination of stimuli is required. The oldest forms of synthetic molecular switches are pH indicators, which display distinct colors as a function of pH. Currently synthetic molecular switches are of interest in the field of nanotechnology for application in molecular computers or responsive drug delivery systems. Molecular switches are also important in biology because many biological functions are based on it, for instance allosteric regulation and vision. They are also one of the simplest examples of molecular machines. Biological molecular switches In cellular biology, proteins act as intracellular signaling molecules by activating another protein i ...
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Macrocycle
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. Synthesis The formation of macrocycles by ring-closure is called macrocylization. Pioneering work was reported for studies on terpenoid macrocycles. The central challenge to macrocyclization is that ring-closing reactions do not favor the formation of large rings. Instead, small rings or polymers tend to form. This kinetic problem can be addressed by using high-dilution reactions, whereby intramolecular processes are favored relative to polymerizations. Some macrocyclizations are favored using template reactions. Templates are ions, molecules, surfaces etc. that bind and pre-organize compounds, guiding them toward formation of a particular ring size. The crown ethers are often generated in the presence of an alkali metal cation, whic ...
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Jeremy Sanders
Jeremy Keith Morris Sanders (born 3 May 1948) is a British chemist and Emeritus Professor in the Department of Chemistry at the University of Cambridge. He is also Editor-in-Chief of Royal Society Open Science. He is known for his contributions to many fields including NMR spectroscopy and supramolecular chemistry. He served as the Pro-Vice-Chancellor for Institutional Affairs at the University of Cambridge, 2011–2015. Education Educated in London at Southmead Primary School and Wandsworth Comprehensive School, he then studied chemistry at Imperial College London where he graduated with a Bachelor of Science degree in 1969 and was awarded the Edmund White Prize. During 1969–72 he carried out his PhD research on lanthanide shift reagents, especially Eu(DPM), the original reagent developed before Eu(FOD) at Churchill College, Cambridge, supervised by Dudley Williams. Career and Research Elected a fellow of Christ's College, Cambridge, in 1972, he spent a postdoct ...
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Azobenzene
Azobenzene is a photoswitchable chemical compound composed of two phenyl rings linked by a N=N double bond. It is the simplest example of an aryl azo compound. The term 'azobenzene' or simply 'azo' is often used to refer to a wide class of similar compounds. These azo compounds are considered as derivatives of diazene (diimide), and are sometimes referred to as 'diazenes'. The diazenes absorb light strongly and are common dyes. Structure and synthesis ''trans''-Azobenzene is planar. The N-N distance is 1.189 Å. ''cis''-Azobenzene is nonplanar with a C-N=N-C dihedral angle of 173.5°. The N-N distance is 1.251 Å. Azobenzene was first described by Eilhard Mitscherlich in 1834. Yellowish-red crystalline flakes of azobenzene were obtained in 1856. Its original preparation is similar to the modern one. According to the 1856 method, nitrobenzene is reduced by iron filings in the presence of acetic acid. In the modern synthesis, zinc is the reductant in the presence of a base. I ...
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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 with sulfur atoms. Over 10,000 scientific publications discuss TTF and its derivatives. Preparation The high level of interest in TTFs has spawned the development of many syntheses of TTF and its analogues. Most preparations entail the coupling of cyclic building blocks such as 1,3-dithiole-2-thion or the related 1,3-dithiole-2-ones. For TTF itself, the synthesis begins with the trithiocarbonate , which is S-methylated and then reduced to give , which is treated as follows: :H2C2S2CH(SCH3) + HBF4 -> 2C2S2CH+F4- + HSCH3 :2 2C2S2CH+F4- + 2 Et3N -> (H2C2S2C)2 + 2 Et3NHBF4 Redox properties Bulk TTF itself has unremarkable electrical properties. Distinctive properties are, however, associated with salts of its oxidized derivatives, suc ...
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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 The viologen paraquat (R = methyl), is a widely used herbicide. As early as in the 1930s, paraquat was being used as an oxidation-reduction indicator, because it becomes violet on reduction. Other viologens have been commercialized because they can change color reversibly many times through reduction and oxidation. The name viologen alludes to violet, one color it can exhibit, and the radical cation (C5H4NR)2+ is colored intensely blue. Types of viologens As bipyridinium derivatives, the viologens are related to 4,4'-bipyridyl. The basic nitrogen centers in these compounds are alkylated to give viologens: :(C5H4N)2 + 2 RX → C5H4NR)2sup>2+(X−)2 The alkylation is a form of quaternization. When the alkylating agent is a small ...
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Pyridinium
Pyridinium refers to the cation . It is the conjugate acid of pyridine. Many related cations are known involving substituted pyridines, e.g. picolines, lutidines, collidines. They are prepared by treating pyridine with acids. As pyridine is often used as an organic base in chemical reactions, pyridinium salts are produced in many acid-base reactions. Its Salt (chemistry), salts are often insoluble in the organic solvent, so Precipitation (chemistry), precipitation of the pyridinium leaving group complex is an indication of the progress of the reaction. Pyridinium cations are aromatic, as determined through Hückel's rule. They are isoelectronic with benzene. ''N''-Alkylpyridinium cations When the acidic proton is replaced by alkyl, the compounds are called ''N''-alkylpyridinium. A simple representative is Methylpyridinium, ''N''-methylpyridinium ([C5H5NCH3]+). These pyridinium intermediates have been used as electrophiles in synthetic organic chemistry to build dearomatized ...
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Thermodynamics
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology. Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines, particularly through the work of French physicist Sadi Carnot (1824) who believed that engine efficiency was the key that could help France win the Napoleonic Wars. Scots-Irish physicist Lord Kelvin was the first to formulate a ...
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