|
Cryptoregiochemistry
Cryptoregiochemistry refers to the site of initial oxidative attack in double bond formation by enzymes such as fatty acid desaturases. This is a mechanistic parameter that is usually determined through the use of kinetic isotope effect experiments, based on the premise that the initial C-H bond cleavage In chemistry, bond cleavage, or bond fission, is the splitting of chemical bonds. This can be generally referred to as dissociation when a molecule is cleaved into two or more fragments. In general, there are two classifications for bond cleavag ... step should be energetically more difficult and therefore more sensitive to isotopic substitution than the second C-H bond breaking step. References Chemical kinetics Stereochemistry {{Chem-stub ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Oxidative
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. There are two classes of redox reactions: * ''Electron-transfer'' – Only one (usually) electron flows from the reducing agent to the oxidant. This type of redox reaction is often discussed in terms of redox couples and electrode potentials. * ''Atom transfer'' – An atom transfers from one substrate to another. For example, in the rusting of iron, the oxidation state of iron atoms increases as the iron converts to an oxide, and simultaneously the oxidation state of oxygen decreases as it accepts electrons released by the iron. Although oxidation reactions are commonly associated with the formation of oxides, other chemical species can serve the same function. In hydrogenation, C=C (and other) bonds ar ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Double Bond
In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist between two different elements: for example, in a carbonyl group between a carbon atom and an oxygen atom. Other common double bonds are found in azo compounds (N=N), imines (C=N), and sulfoxides (S=O). In a skeletal formula, a double bond is drawn as two parallel lines (=) between the two connected atoms; typographically, the equals sign is used for this. Double bonds were first introduced in chemical notation by Russian chemist Alexander Butlerov. Double bonds involving carbon are stronger and shorter than single bonds. The bond order is two. Double bonds are also electron-rich, which makes them potentially more reactive in the presence of a strong electron acceptor (as in addition reactions of the halogens). File:Ethene structural.svg ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enzyme
Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products. Almost all metabolic processes in the cell need enzyme catalysis in order to occur at rates fast enough to sustain life. Metabolic pathways depend upon enzymes to catalyze individual steps. The study of enzymes is called ''enzymology'' and the field of pseudoenzyme analysis recognizes that during evolution, some enzymes have lost the ability to carry out biological catalysis, which is often reflected in their amino acid sequences and unusual 'pseudocatalytic' properties. Enzymes are known to catalyze more than 5,000 biochemical reaction types. Other biocatalysts are catalytic RNA molecules, called ribozymes. Enzymes' specificity comes from their unique three-dimensional structures. Like all catalysts, enzymes increase the reaction ra ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Fatty Acid
In chemistry, particularly in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, from 4 to 28. Fatty acids are a major component of the lipids (up to 70% by weight) in some species such as microalgae but in some other organisms are not found in their standalone form, but instead exist as three main classes of esters: triglycerides, phospholipids, and cholesteryl esters. In any of these forms, fatty acids are both important dietary sources of fuel for animals and important structural components for cells. History The concept of fatty acid (''acide gras'') was introduced in 1813 by Michel Eugène Chevreul, though he initially used some variant terms: ''graisse acide'' and ''acide huileux'' ("acid fat" and "oily acid"). Types of fatty acids Fatty acids are classified in many ways: by length, by saturation vs unsaturati ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Desaturase
A fatty acid desaturase is an enzyme that removes two hydrogen atoms from a fatty acid, creating a carbon/carbon double bond. These desaturases are classified as: * Delta - indicating that the double bond is created at a fixed position from the carboxyl end of a fatty acid chain. For example, Δ9 desaturase creates a double bond between the ninth and tenth carbon atom from the carboxyl end. * Omega - indicating the double bond is created at a fixed position from the methyl end of a fatty acid chain. For instance, ω3 desaturase creates a double bond between the third and fourth carbon atom from the methyl end. In other words, it creates an omega-3 fatty acid. For example, Δ6 desaturation introduces a double bond between carbons 6 and 7 of Linoleic acid (LA C18H32O2; 18:2-n6) and α-Linolenic acid (ALA: C18H30O2; 18:3-n3), creating ''γ''-linolenic acid (GLA: C18H30O2,18:3-n6) and stearidonic acid (SDA: C18H28O2; 18:4-n3) respectively. In humans, Δ17-desaturase is able to tur ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Kinetic Isotope Effect
In physical organic chemistry, a kinetic isotope effect (KIE) is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants for the reactions involving the light (''kL'') and the heavy (''kH'') isotopically substituted reactants (isotopologues): :\text=\frac This change in reaction rate is a quantum mechanical effect that primarily results from heavier isotopologues having lower vibrational frequencies compared to their lighter counterparts. In most cases, this implies a greater energetic input needed for heavier isotopologues to reach the transition state (or, in rare cases, the dissociation limit), and consequently, a slower reaction rate. The study of kinetic isotope effects can help the elucidation of the reaction mechanism of certain chemical reactions and is occasionally exploited in drug development to improve unfavorable pharmacokinetics by protecting m ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bond Cleavage
In chemistry, bond cleavage, or bond fission, is the splitting of chemical bonds. This can be generally referred to as dissociation when a molecule is cleaved into two or more fragments. In general, there are two classifications for bond cleavage: ''homo''lytic and ''hetero''lytic, depending on the nature of the process. The triplet and singlet excitation energies of a sigma bond can be used to determine if a bond will follow the homolytic or heterolytic pathway. A metal−metal sigma bond is an exception because the bond's excitation energy is extremely high, thus cannot be used for observation purposes. In some cases, bond cleavage requires catalysts. Due to the high bond-dissociation energy of C-H bonds, around , a large amount of energy is required to cleave the hydrogen atom from the carbon and bond a different atom to the carbon. Homolytic cleavage In homolytic cleavage, or homolysis, the two electrons in a cleaved covalent bond are divided equally between th ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Isotopic Substitution
In chemistry, isotopologues are molecules that differ only in their isotopic composition. They have the same chemical formula and bonding arrangement of atoms, but at least one atom has a different number of neutrons than the parent. An example is water, whose hydrogen-related isotopologues are: "light water" (HOH or ), " semi-heavy water" with the deuterium isotope in equal proportion to protium (HDO or ), " heavy water" with two deuterium isotopes of hydrogen per molecule ( or ), and "super-heavy water" or tritiated water ( or , as well as and , where some or all of the hydrogen atoms are replaced with the radioactive tritium isotope). Oxygen-related isotopologues of water include the commonly available form of heavy-oxygen water () and the more difficult to separate version with the isotope. Both elements may be replaced by isotopes, for example in the doubly labeled water isotopologue . All taken together, there are 9 different stable water isotopologues, and 9 radioactiv ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
_(2).png "Click for more on -> Kinetic Isotope Effect")
_V.1.svg "Click for more on -> Bond Cleavage")