Spontaneous Absolute Asymmetric Synthesis
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Spontaneous Absolute Asymmetric Synthesis
Spontaneous absolute asymmetric synthesis is a chemical phenomenon that ''stochastically'' generates chirality based on autocatalysis and small fluctuations in the ratio of enantiomers present in a racemic mixture.Tsuneomi Kawasaki, Kenta Suzuki, Masako Shimizu, Keisuke Ishikawa and Kenso Soai, ''Chirality'', Volume 18, Issue 7, pages 479–482, 2006, In certain reactions which initially do not contain chiral information, stochastically distributed enantiomeric excess can be observed. The phenomenon is different from chiral amplification, where enantiomeric excess is present from the beginning and not stochastically distributed. Hence, when the experiment is repeated many times, the average enantiomeric excess approaches 0%.Kenta Suzuki, Kunihiko Hatase, Daisuke Nishiyama, Tsuneomi Kawasaki, Kenso Soai, ''Journal of Systems Chemistry'' 2010, 1:5 (18 August 2010), The phenomenon has important implications concerning the origin of homochirality in nature.{{cite journal , journal= Hi ...
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Stochastic
Stochastic (, ) refers to the property of being well described by a random probability distribution. Although stochasticity and randomness are distinct in that the former refers to a modeling approach and the latter refers to phenomena themselves, these two terms are often used synonymously. Furthermore, in probability theory, the formal concept of a ''stochastic process'' is also referred to as a ''random process''. Stochasticity is used in many different fields, including the natural sciences such as biology, chemistry, ecology, neuroscience, and physics, as well as technology and engineering fields such as image processing, signal processing, information theory, computer science, cryptography, and telecommunications. It is also used in finance, due to seemingly random changes in financial markets as well as in medicine, linguistics, music, media, colour theory, botany, manufacturing, and geomorphology. Etymology The word ''stochastic'' in English was originally used as a ...
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Chirality
Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from its mirror image; that is, it cannot be superimposed onto it. Conversely, a mirror image of an ''achiral'' object, such as a sphere, cannot be distinguished from the object. A chiral object and its mirror image are called ''enantiomorphs'' (Greek, "opposite forms") or, when referring to molecules, '' enantiomers''. A non-chiral object is called ''achiral'' (sometimes also ''amphichiral'') and can be superposed on its mirror image. The term was first used by Lord Kelvin in 1893 in the second Robert Boyle Lecture at the Oxford University Junior Scientific Club which was published in 1894: Human hands are perhaps the most recognized example of chirality. The left hand is a non-superimposable mirror image of the right hand; no matter ho ...
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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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Enantiomer
In chemistry, an enantiomer ( /ɪˈnænti.əmər, ɛ-, -oʊ-/ ''ih-NAN-tee-ə-mər''; from Ancient Greek ἐνάντιος ''(enántios)'' 'opposite', and μέρος ''(méros)'' 'part') – also called optical isomer, antipode, or optical antipode – is one of two stereoisomers that are non-superposable onto their own mirror image. Enantiomers are much like one's right and left hands, when looking at the same face, they cannot be superposed onto each other. No amount of reorientation will allow the four unique groups on the chiral carbon (see Chirality (chemistry)) to line up exactly. The number of stereoisomers a molecule has can be determined by the number of chiral carbons it has. Stereoisomers include both enantiomers and diastereomers. Diastereomers, like enantiomers, share the same molecular formula and are non-superposable onto each other however, they are not mirror images of each other. A molecule with chirality rotates plane-polarized light. A mixture of equals a ...
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Racemic Mixture
In chemistry, a racemic mixture, or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates. History The first known racemic mixture was racemic acid, which Louis Pasteur found to be a mixture of the two enantiomeric isomers of tartaric acid. He manually separated the crystals of a mixture by hand, starting from an aqueous solution of the sodium ammonium salt of racemate tartaric acid. Pasteur benefited from the fact that ammonium tartrate salt that gives enantiomeric crystals with distinct crystal forms (at 77 °F). Reasoning from the macroscopic scale down to the molecular, he reckoned that the molecules had to have non-superimposable mirror images. A sample with only a single enantiomer is an ''enantiomerically pure'' or ''enantiopure'' compound. Etymology From racemic acid found in grapes; from Latin ''racemus'', meani ...
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Chiral Information
Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from its mirror image; that is, it cannot be superimposed onto it. Conversely, a mirror image of an ''achiral'' object, such as a sphere, cannot be distinguished from the object. A chiral object and its mirror image are called ''enantiomorphs'' (Greek, "opposite forms") or, when referring to molecules, ''enantiomers''. A non-chiral object is called ''achiral'' (sometimes also ''amphichiral'') and can be superposed on its mirror image. The term was first used by Lord Kelvin in 1893 in the second Robert Boyle Lecture at the Oxford University Junior Scientific Club which was published in 1894: Human hands are perhaps the most recognized example of chirality. The left hand is a non-superimposable mirror image of the right hand; no matter how the ...
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Enantiomeric Excess
In stereochemistry, enantiomeric excess (ee) is a measurement of purity used for chiral substances. It reflects the degree to which a sample contains one enantiomer in greater amounts than the other. A racemic mixture has an ee of 0%, while a single completely pure enantiomer has an ee of 100%. A sample with 70% of one enantiomer and 30% of the other has an ee of 40% (70% − 30%). Definition Enantiomeric excess is defined as the absolute difference between the mole fraction of each enantiomer: :\ ee = , F_R - F_S, where :\ F_R + F_S = 1 In practice, it is most often expressed as a percent enantiomeric excess. The enantiomeric excess can be determined in another way if we know the amount of each enantiomer produced. If one knows the moles of each enantiomer produced then: Enantiomeric excess is used as one of the indicators of the success of an asymmetric synthesis. For mixtures of diastereomers, there are analogous definitions and uses for diastereomeric excess an ...
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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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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 stereoisomers, which by definition have the same molecular formula and sequence of bonded atoms (constitution), but differ in structural formula (the three-dimensional orientations of their atoms in space). For this reason, it is also known as 3D chemistry—the prefix "stereo-" means "three-dimensionality". Stereochemistry spans the entire spectrum of organic, inorganic, biological, physical and especially supramolecular chemistry. Stereochemistry includes methods for determining and describing these relationships; the effect on the physical or biological properties these relationships impart upon the molecules in question, and the manner in which these relationships influence the reactivity of the molecules in question ( dynamic stereochemis ...
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Biological Processes
Biological processes are those processes that are vital for an organism to live, and that shape its capacities for interacting with its environment. Biological processes are made of many chemical reactions or other events that are involved in the persistence and transformation of life forms. Metabolism and homeostasis are examples. Biological processes within an organism can also work as bioindicators. Scientists are able to look at an individual's biological processes to monitor the effects of environmental changes. Regulation of biological processes occurs when any process is modulated in its frequency, rate or extent. Biological processes are regulated by many means; examples include the control of gene expression, protein modification or interaction with a protein or substrate molecule. * Homeostasis: regulation of the internal environment to maintain a constant state; for example, sweating to reduce temperature * Organization: being structurally composed of one or more cell ...
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