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Non-linear Effects
In enantioselective synthesis, a non-linear effect refers to a process in which the enantiopurity of the catalyst or chiral auxiliary does not correspond with the enantiopurity of the product produced. For example: a racemic catalyst would be expected to convert a prochiral substrate into a racemic product (a linear effect), but this is not always the case and a chirally enriched product can be produced instead (a non-linear effect). This can be expressed mathematically, as shown in Equation 1. Stereoselection that is higher or lower than the enantiomeric excess of the catalyst is considered non-ideal behavior. In non-ideal behavior, this deviation from linearity is described as the non-linear effect, NLE. :ee_\text=ee_ee_\text For an ideal asymmetric reaction, the eeproduct may be described as the product of eemax multiplied by the eecatalyst. ''This is not the case for reactions exhibiting NLE's.'' Non-linear effects often arise in reactions with a scalemic catalyst composition. ...
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Enantioselective Synthesis
Enantioselective synthesis, also called asymmetric synthesis, is a form of chemical synthesis. It is defined by IUPAC as "a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecule and which produces the stereoisomeric (enantiomeric or diastereomeric) products in unequal amounts." Put more simply: it is the synthesis of a compound by a method that favors the formation of a specific enantiomer or diastereomer. Enantiomers are stereoisomers that have opposite configurations at every chiral center. Diastereomers are stereoisomers that differ at one or more chiral centers. Enantioselective synthesis is a key process in modern chemistry and is particularly important in the field of pharmaceuticals, as the different enantiomers or diastereomers of a molecule often have different biological activity. Overview Many of the building blocks of biological systems such as sugars and amino acids are produced exclusively as ...
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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 towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant. A knowledge of equilibrium constants is essential for the understanding of many chemical systems, as well as biochemical processes such as oxygen transport by hemoglobin in blood and acid–base homeostasis in the human body. Stability constants, formation cons ...
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Homochirality
Homochirality is a uniformity of chirality, or handedness. Objects are chiral when they cannot be superposed on their mirror images. For example, the left and right hands of a human are approximately mirror images of each other but are not their own mirror images, so they are chiral. In biology, 19 of the 20 natural amino acids are homochiral, being L-chiral (left-handed), while sugars are D-chiral (right-handed). Homochirality can also refer to enantiopure substances in which all the constituents are the same enantiomer (a right-handed or left-handed version of an atom or molecule), but some sources discourage this use of the term. It is unclear whether homochirality has a purpose; however, it appears to be a form of information storage. One suggestion is that it reduces entropy barriers in the formation of large organized molecules. It has been experimentally verified that amino acids form large aggregates in larger abundance from an enantiopure samples of the amino acid than fr ...
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Autocatalysis
A single chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same or a coupled reaction.Steinfeld J.I., Francisco J.S. and Hase W.L. ''Chemical Kinetics and Dynamics'' (2nd ed., Prentice-Hall 1999) p.151-2 Such a reaction is called an autocatalytic reaction. A ''set'' of chemical reactions can be said to be "collectively autocatalytic" if a number of those reactions produce, as reaction products, catalysts for enough of the other reactions that the entire set of chemical reactions is self-sustaining given an input of energy and food molecules (see autocatalytic set). Chemical reactions A chemical reaction of two reactants and two products can be written as : \alpha A + \beta B \rightleftharpoons \sigma S + \tau T where the Greek letters are stoichiometric coefficients and the capital Latin letters represent chemical species. The chemical reaction proceeds in both the forward and reverse direction. This equation is easily g ...
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Chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during a Chemical reaction, reaction with other Chemical substance, substances. Chemistry also addresses the nature of chemical bonds in chemical compounds. In the scope of its subject, chemistry occupies an intermediate position between physics and biology. It is sometimes called the central science because it provides a foundation for understanding both Basic research, basic and Applied science, applied scientific disciplines at a fundamental level. For example, chemistry explains aspects of plant growth (botany), the formation of igneous rocks (geology), how atmospheric ozone is formed and how environmental pollutants are degraded (ecology), the properties ...
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Sulfide
Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH−) are the conjugate acids of sulfide. Chemical properties The sulfide ion, S2−, does not exist in aqueous alkaline solutions of Na2S. Instead sulfide converts to hydrosulfide: :S2− + H2O → SH− + OH− Upon treatment with an acid, sulfide salts convert to hydrogen sulfide: :S2− + H+ → SH− :SH− + H+ → H2S Oxidation of sulfide is a complicated process. Depending on the conditions, the oxidation can produce elemental sulfur, polysulfides, polythionates, sulfite, or sulfate. Metal sulfides react with halogens, forming sulfur and metal salts. :8 MgS + 8 I2 → S8 + 8 M ...
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Sharpless Geraniol Reaction
Sharpless is a surname. Notable people with the surname include: *Bevan Sharpless, solar system astronomer *Karl Barry Sharpless, American chemist and Nobel prize winner *Josh Sharpless, baseball player *Christopher Sharpless, 1988 Winter Olympics bobsledder * Mattie R. Sharpless (born 1942), American diplomat *Stewart Sharpless, galactic astronomer **Sharpless catalog, a 20th-century astronomical catalog with 313 items *Isaac Sharpless, educator *Norman Sharpless, American oncologist and director of the National Cancer Institute *Disappearance of Toni Sharpless, an American nurse who disappeared in 2009 Fictional characters *A character in Madama Butterfly See also *Sharpless asymmetric dihydroxylation, a chemical reaction *Sharpless epoxidation, a chemical reaction *Sharpless oxyamination The Sharpless oxyamination (often known as Sharpless aminohydroxylation) is the chemical reaction that converts an alkene to a vicinal amino alcohol. The reaction is related to the Sharpless d ...
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Monomeric
In chemistry, a monomer ( ; ''mono-'', "one" + ''-mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization. Classification Monomers can be classified in many ways. They can be subdivided into two broad classes, depending on the kind of the polymer that they form. Monomers that participate in condensation polymerization have a different stoichiometry than monomers that participate in addition polymerization: : Other classifications include: *natural vs synthetic monomers, e.g. glycine vs caprolactam, respectively *polar vs nonpolar monomers, e.g. vinyl acetate vs ethylene, respectively *cyclic vs linear, e.g. ethylene oxide vs ethylene glycol, respectively The polymerization of one kind of monomer gives a homopolymer. Many polymers are copolymers, meaning that they are derived from two different monomers. In the case of condensation polymerizations, the rat ...
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Dimer (chemistry)
A dimer () ('' di-'', "two" + ''-mer'', "parts") is an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. Dimers also have significant implications in polymer chemistry, inorganic chemistry, and biochemistry. The term ''homodimer'' is used when the two molecules are identical (e.g. A–A) and ''heterodimer'' when they are not (e.g. A–B). The reverse of dimerization is often called dissociation. When two oppositely charged ions associate into dimers, they are referred to as ''Bjerrum pairs'', after Niels Bjerrum. Noncovalent dimers Anhydrous carboxylic acids form dimers by hydrogen bonding of the acidic hydrogen and the carbonyl oxygen. For example, acetic acid forms a dimer in the gas phase, where the monomer units are held together by hydrogen bonds. Under special conditions, most OH-containing molecules form dimers, e.g. the water dimer. Excimers and exciplexes are excited structures with a short lifetime. ...
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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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