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Cyclobis(paraquat-p-phenylene)
Cyclobis(paraquat-''p''-phenylene) (formally a derivative of paraquat) belongs to the class of cyclophanes, and consists of aromatic units connected by methylene bridges. It is able to incorporate small guest molecule and has played an important role in host–guest chemistry and supramolecular chemistry. The cyclophane is also referred to as ''Stoddart's blue box'' because its inventor, J. Fraser Stoddart, illustrates the electron-poor areas of molecules in a blue shade. Synthesis For synthesis of cyclobis(paraquat-''p''-phenylene), 4,4'-bipyridine is reacted with 1,4-bis(bromomethyl)benzene to 1,1′- ,4-phenylenebis-(methylene)is(4,4′-bipyridine), which is reacted in a template synthesis again with 4,4′-bipyridine to the final product. A common template for this synthesis is 1,5-bis -(2-methoxyethoxy)ethoxyaphthalene. : Host guest chemistry Cyclobis(paraquat-''p''-phenylene) is able to incorporate small guest molecules forming a host–guest complex. The interactio ...
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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., . Important members of this series are the tetramer (''n'' = 4), the pentamer (''n'' = 5), and the hexamer (''n'' = 6). The term "crown" refers to the resemblance between the structure of a crown ether bound to a cation, and a crown sitting on a person's head. The first number in a crown ether's name refers to the number of atoms in the cycle, and the second number refers to the number of those atoms that are oxygen. Crown ethers are much broader than the oligomers of ethylene oxide; an important group are derived from catechol. Crown ethers strongly bind certain cations, forming complexes. The oxygen atoms are well situated to coordinate with a cation located at the interior of the ring, whereas the exterior of t ...
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Catenanes
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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Host–guest Chemistry
In supramolecular chemistry, host–guest chemistry describes 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 bonds. Host–guest chemistry encompasses the idea of molecular recognition and interactions through non-covalent bonding. Non-covalent bonding is critical in maintaining the 3D structure of large molecules, such as proteins and is involved in many biological processes in which large molecules bind specifically but transiently to one another. Although non-covalent interactions could be roughly divided into those with more electrostatic or dispersive contributions, there are few commonly mentioned types of non-covalent interactions: ionic bonding, hydrogen bonding, van der Waals forces and hydrophobic interactions. Overview Host–guest chemistry is a branch of supramolecular chemistry in which a host molecule forms a chemical compound with a guest molecul ...
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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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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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Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction. History In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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Hexafluorophosphate
Hexafluorophosphate is an anion with chemical formula of . It is an octahedral species that imparts no color to its salts. is isoelectronic with sulfur hexafluoride, , and the hexafluorosilicate dianion, , and hexafluoroantimonate . In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion. Synthesis Hexafluorophosphate salts can be prepared by the reaction of phosphorus pentachloride and alkali or ammonium halide in a solution of hydrofluoric acid: : Hexafluorophosphoric acid can be prepared by direct reaction of hydrogen fluoride with phosphorus pentafluoride. It is a strong Brønsted acid that is typically generated ''in situ'' immediately before its use. : These reactions require specialized equipment to safely handle the hazards associated with hydrofluoric acid and hydrogen fluoride. Quantitative analysis Several methods of quantitative analysis for the hexafluorophosphate ion have been de ...
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Counterion
160px, Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion.">cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion. In chemistry, a counterion (sometimes written as "counter ion", pronounced as such) is the ion that accompanies an Ionic compound, ionic species in order to maintain Electric charge, electric neutrality. In table salt (NaCl, also known as sodium chloride) the sodium ion (positively charged) is the counterion for the chloride ion (negatively charged) and vice versa. A counterion will be more commonly referred to as an anion or a cation, depending on whether it is negatively or positively charged. Thus, the counterion to an anion will be a cation, and vice versa. In biochemistry, counterions are generally vaguely defined. Depending on their charge, proteins are associated with a variety of smaller ani ...
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Solvophobic Forces
Solvophobic theory attempts to explain interactions between polar solvents and non-polar solutes. In the pure solvent, there are relatively strong cohesive forces between the solvent molecules due to hydrogen bonding or other polar interactions. Hence, non-polar solutes tend not to be soluble in polar solvents because these solvent-solvent binding interactions must be overcome first. When applied to liquid chromatography In chemical analysis, chromatography is a laboratory technique for the Separation process, separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it ... (LC), solvophobic theory attributes the retention of solutes on the stationary phase partly to the rejection of solute molecules by the solvent, and partly to the attraction of the solute molecules by the stationary phase.Satinder Ahuja, Selectivity and detectability optimizations in HPLC , References Solutions C ...
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Association Constant
The binding constant, or affinity constant/association constant, is a special case of the equilibrium constant ''K'', and is the inverse of the dissociation constant. It is associated with the binding and unbinding reaction of receptor (R) and ligand (L) molecules, which is formalized as: :R + L RL The reaction is characterized by the on-rate constant ''k''on and the off-rate constant ''k''off, which have units of M−1 s−1 and s−1, respectively. In equilibrium, the forward binding transition R + L → RL should be balanced by the backward unbinding transition RL → R + L. That is, :k_\,[]\,[] = k_\,[], where [R], [L] and [RL] represent the concentration of unbound free receptors, the concentration of unbound free ligand and the concentration of receptor-ligand complexes. The binding constant ''K''a is defined by :K_ = = . An often considered quantity is the dissociation constant ''K''d ≡ , which has the unit of concentration, despite the fact that str ...
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Spectroscopic
Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO) In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum. Historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of astronomy, chemistry, materials science, and physics, allowing the composition, physical structure and elec ...
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