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Reaction Progress Kinetic Analysis
In chemistry, reaction progress kinetic analysis (RPKA) is a subset of a broad range of kinetic techniques utilized to determine the rate laws of chemical reactions and to aid in elucidation of reaction mechanisms. While the concepts guiding reaction progress kinetic analysis are not new, the process was formalized by Professor Donna Blackmond (currently at Scripps Research Institute) in the late 1990s and has since seen increasingly widespread use. Unlike more common pseudo-first-order analysis, in which an overwhelming excess of one or more reagents is used relative to a species of interest, RPKA probes reactions at synthetically relevant conditions (i.e. with concentrations and reagent ratios resembling those used in the reaction when not exploring the rate law.) Generally, this analysis involves a system in which the concentrations of ''multiple'' reactants are changing measurably over the course of the reaction. As the mechanism can vary depending on the relative and absolute ...
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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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Infrared
Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around 1 millimeter (300 GHz) to the nominal red edge of the visible spectrum, around 700  nanometers (430  THz). Longer IR wavelengths (30 μm-100 μm) are sometimes included as part of the terahertz radiation range. Almost all black-body radiation from objects near room temperature is at infrared wavelengths. As a form of electromagnetic radiation, IR propagates energy and momentum, exerts radiation pressure, and has properties corresponding to both those of a wave and of a particle, the photon. It was long known that fires emit invisible heat; in 1681 the pioneering experimenter Edme Mariotte showed that glass, though transparent to sunlight, obstructed radiant heat. In 1800 the astronomer Sir William Herschel discovered ...
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Calorimetry
In chemistry and thermodynamics, calorimetry () is the science or act of measuring changes in ''state variables'' of a body for the purpose of deriving the heat transfer associated with changes of its state due, for example, to chemical reactions, physical changes, or phase transitions under specified constraints. Calorimetry is performed with a calorimeter. Scottish physician and scientist Joseph Black, who was the first to recognize the distinction between heat and temperature, is said to be the founder of the science of calorimetry. Indirect calorimetry calculates heat that living organisms produce by measuring either their production of carbon dioxide and nitrogen waste (frequently ammonia in aquatic organisms, or urea in terrestrial ones), or from their consumption of oxygen. Lavoisier noted in 1780 that heat production can be predicted from oxygen consumption this way, using multiple regression. The dynamic energy budget theory explains why this procedure is correct. He ...
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Barbier Reaction
The Barbier reaction is an organometallic reaction between an alkyl halide (chloride, bromide, iodide), a carbonyl group and a metal. The reaction can be performed using magnesium, aluminium, zinc, indium, tin, samarium, barium or their salts. The reaction product is a primary, secondary or tertiary alcohol. The reaction is similar to the Grignard reaction but the crucial difference is that the organometallic species in the Barbier reaction is generated ''in situ'', whereas a Grignard reagent is prepared separately before addition of the carbonyl compound. Unlike many Grignard reagents, the organometallic species generated in a Barbier reaction are unstable and thus cannot be stored or sold commercially. Barbier reactions are nucleophilic addition reactions that involve relatively inexpensive, water insensitive metals (e.g zinc powder) or metal compounds. For this reason it is possible in many cases to run the reaction in water, making the procedure part of green chemistry. In cont ...
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Samarium
Samarium is a chemical element with symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of samarium(II) are also known, most notably the monoxide SmO, monochalcogenides SmS, SmSe and SmTe, as well as samarium(II) iodide. The last compound is a common reducing agent in chemical synthesis. Samarium has no significant biological role, and some samarium salts are slightly toxic. Samarium was discovered in 1879 by French chemist Paul-Émile Lecoq de Boisbaudran and named after the mineral samarskite from which it was isolated. The mineral itself was named after a Russian mine official, Colonel Vassili Samarsky-Bykhovets, who thus became the first person to have a chemical element named after him, albeit indirectly. Though classified as a rare-earth element, samarium is the 40th most abundant element in Earth's crust and more common than ...
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Proceedings Of The National Academy Of Sciences Of The United States Of America
''Proceedings of the National Academy of Sciences of the United States of America'' (often abbreviated ''PNAS'' or ''PNAS USA'') is a peer-reviewed multidisciplinary scientific journal. It is the official journal of the National Academy of Sciences, published since 1915, and publishes original research, scientific reviews, commentaries, and letters. According to ''Journal Citation Reports'', the journal has a 2021 impact factor of 12.779. ''PNAS'' is the second most cited scientific journal, with more than 1.9 million cumulative citations from 2008 to 2018. In the mass media, ''PNAS'' has been described variously as "prestigious", "sedate", "renowned" and "high impact". ''PNAS'' is a delayed open access journal, with an embargo period of six months that can be bypassed for an author fee ( hybrid open access). Since September 2017, open access articles are published under a Creative Commons license. Since January 2019, ''PNAS'' has been online-only, although print issues are ava ...
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Ether
In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be classified into two varieties: if the alkyl or aryl groups are the same on both sides of the oxygen atom, then it is a simple or symmetrical ether, whereas if they are different, the ethers are called mixed or unsymmetrical ethers. A typical example of the first group is the solvent and anaesthetic diethyl ether, commonly referred to simply as "ether" (). Ethers are common in organic chemistry and even more prevalent in biochemistry, as they are common linkages in carbohydrates and lignin. Structure and bonding Ethers feature bent C–O–C linkages. In dimethyl ether, the bond angle is 111° and C–O distances are 141  pm. The barrier to rotation about the C–O bonds is low. The bonding of oxygen in ethers, alcohols, and water is ...
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Iodolactonization
Iodolactonization (or, more generally, halolactonization) is an organic reaction that forms a ring (the lactone) by the addition of an oxygen and iodine across a carbon-carbon double bond. It is an intramolecular variant of the halohydrin synthesis reaction. The reaction was first reported by M. J. Bougalt in 1904 and has since become one of the most effective ways to synthesize lactones. Strengths of the reaction include the mild conditions and incorporation of the versatile iodine atom into the product. : Iodolactonization has been used in the synthesis of many natural products including those with medicinal applications such as vernolepin and vernomenin, two compounds used in tumor growth inhibition, and vibralactone, a pancreatic lipase inhibitor. Iodolactonization has also been used by Elias James Corey to synthesize numerous prostaglandins. History Sandra's report of iodolactonization represented the first example of a reliable lactonization that could be used in many dif ...
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Lewis Base
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane (Me3B) is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis. From p. 142: "We are inclined to think of substances as pos ...
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Amino Acids
Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although hundreds of amino acids exist in nature, by far the most important are the alpha-amino acids, which comprise proteins. Only 22 alpha amino acids appear in the genetic code. Amino acids can be classified according to the locations of the core structural functional groups, as Alpha and beta carbon, alpha- , beta- , gamma- or delta- amino acids; other categories relate to Chemical polarity, polarity, ionization, and side chain group type (aliphatic, Open-chain compound, acyclic, aromatic, containing hydroxyl or sulfur, etc.). In the form of proteins, amino acid '' residues'' form the second-largest component (water being the largest) of human muscles and other tissues. Beyond their role as residues in proteins, amino acids participate in a number of processes such as neurotransmitter transport and biosynthesis. It is thought that they played a key role in enabling lif ...
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Strecker Synthesis
The Strecker amino acid synthesis, also known simply as the Strecker synthesis, is a method for the synthesis of amino acids by the reaction of an aldehyde with ammonia in the presence of potassium cyanide. The condensation reaction yields an α-aminonitrile, which is subsequently hydrolyzed to give the desired amino acid. The method is used commercially for the production of racemic methionine from methional. While usage of ammonium salts gives unsubstituted amino acids, primary and secondary amines also give substituted amino acids. Likewise, the usage of ketones, instead of aldehydes, gives α,α-disubstituted amino acids. Reaction mechanism In the first part of the reaction, the carbonyl oxygen of an aldehyde is protonated, followed by a nucleophilic attack of ammonia to the carbonyl carbon. After subsequent proton exchange, water is cleaved from the iminium ion intermediate. A cyanide ion then attacks the iminium carbon yielding an aminonitrile. In the second part of th ...
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