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Photolabile Protecting Group
A photolabile protecting group (PPG; also known as: photoremovable, photosensitive, or photocleavable protecting group) is a chemical modification to a molecule that can be removed with light. PPGs enable high degrees of chemoselectivity as they allow researchers to control spatial, temporal and concentration variables with light. Control of these variables is valuable as it enables multiple PPG applications, including orthogonality in systems with multiple protecting groups. As the removal of a PPG does not require chemical reagents, the photocleavage of a PPG is often referred to as "traceless reagent processes", and is often used in biological model systems and multistep organic syntheses. Since their introduction in 1962, numerous PPGs have been developed and utilized in a variety of wide-ranging applications from protein science to photoresists. Due to the large number of reported protecting groups, PPGs are often categorized by their major functional group(s); three of the mo ...
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Molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and ''molecule'' is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.g. water (two hydrogen atoms and one oxygen atom; H2O). In the kinetic theory of gases, the term ''molecule'' is often used for any gaseous particle regardless of its composition. This relaxes the requirement that a molecule contains two or more atoms, since the noble gases are individual atoms. Atoms and complexes connected by non-covalent interactions, such as hydrogen bonds or ionic bonds, are typically not consid ...
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Absorption Spectroscopy
Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum. Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet–visible spectroscopy are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing. There is a wide range of experimental approaches for measuring absorption spectra. The most common arrangement is to direct ...
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Ring (chemistry)
In chemistry, a ring is an ambiguous term referring either to a simple cycle of atoms and bonds in a molecule or to a connected set of atoms and bonds in which every atom and bond is a member of a cycle (also called a ring system). A ring system that is a simple cycle is called a monocycle or simple ring, and one that is not a simple cycle is called a polycycle or polycyclic ring system. A simple ring contains the same number of sigma bonds as atoms, and a polycyclic ring system contains more sigma bonds than atoms. A molecule containing one or more rings is called a cyclic compound, and a molecule containing two or more rings (either in the same or different ring systems) is termed a polycyclic compound. A molecule containing no rings is called an acyclic or open-chain compound. Homocyclic and heterocyclic rings A homocycle or homocyclic ring is a ring in which all atoms are of the same chemical element. A heterocycle or heterocyclic ring is a ring containing atoms of at least ...
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Benzyl Group
In organic chemistry, benzyl is the substituent or molecular fragment possessing the structure . Benzyl features a benzene ring () attached to a methylene group () group. Nomenclature In IUPAC nomenclature, the prefix benzyl refers to a substituent, for example benzyl chloride or benzyl benzoate. Benzyl is not to be confused with phenyl with the formula . The term benzylic is used to describe the position of the first carbon bonded to a benzene or other aromatic ring. For example, is referred to as a "benzylic" carbocation. The benzyl free radical has the formula . The benzyl cation or phenylcarbenium ion is the carbocation with formula ; the benzyl anion or phenylmethanide ion is the carbanion with the formula . None of these species can be formed in significant amounts in the solution phase under normal conditions, but they are useful referents for discussion of reaction mechanisms and may exist as reactive intermediates. Abbreviations The abbreviation "Bn" denotes ben ...
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Radical (chemistry)
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes. A notable example of a radical is the hydroxyl radical (HO·), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene (꞉) which have two unpaired electrons. Radicals may be generated in a number of ways, but typical methods involve redox reactions. Ionizing radiation, heat, electrical discharges, and electrolysis are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations. Radicals are important in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes. A majority of ...
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Excited State
In quantum mechanics, an excited state of a system (such as an atom, molecule or nucleus) is any quantum state of the system that has a higher energy than the ground state (that is, more energy than the absolute minimum). Excitation refers to an increase in energy level above a chosen starting point, usually the ground state, but sometimes an already excited state. The temperature of a group of particles is indicative of the level of excitation (with the notable exception of systems that exhibit negative temperature). The lifetime of a system in an excited state is usually short: spontaneous or induced emission of a quantum of energy (such as a photon or a phonon) usually occurs shortly after the system is promoted to the excited state, returning the system to a state with lower energy (a less excited state or the ground state). This return to a lower energy level is often loosely described as decay and is the inverse of excitation. Long-lived excited states are often called ...
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Diradical
In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate. The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and in fact rarely isolated. Diradicals are even-electron molecules but have one fewer bond than the number permitted by the octet rule. Examples of diradical species can also be found in coordination chemistry, for example among bis(1,2-dithiolene) metal complexes. Spin states Diradicals are usually triplets. The phrases ''singlet'' and ''triplet'' are derived from the multiplicity of states of diradicals in electron spin resonance: a singlet diradical has one state (S = 0, Ms = 2*0+1 = 1, ms = 0) and exhibits no signal in EPR and a triplet diradical has 3 states (S = 1, Ms = 2*1+1 = 3, ms = -1; 0; 1) and shows in EPR 2 peaks (if no hyperfine splitting). The triplet state has total spin quantum number S = 1 and is paramagnetic. Therefore, di ...
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Nitro Compound
In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nitro group is also strongly electron-withdrawing. Because of this property, bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid. Synthesis Preparation of aromatic nitro compounds Aromatic nitro compounds are typically synthesized by nitration. Nitration is achieved using a mixture of nitric acid and sulfuric acid, which produce the nitronium ion (), which is the electrophile:  +    The nitration product produced on the la ...
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Pi Bond
In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals has an electron density of zero at a shared nodal plane that passes through the two bonded nuclei. This plane also is a nodal plane for the molecular orbital of the pi bond. Pi bonds can form in double and triple bonds but do not form in single bonds in most cases. The Greek letter π in their name refers to p orbitals, since the orbital symmetry of the pi bond is the same as that of the p orbital when seen down the bond axis. One common form of this sort of bonding involves p orbitals themselves, though d orbitals also engage in pi bonding. This latter mode forms part of the basis for metal-metal multiple bonding. Pi bonds are usually weaker than sigma bonds. The C-C double bond, composed of one sigma and one pi bond, has a bon ...
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Photon
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless, so they always move at the speed of light in vacuum, (or about ). The photon belongs to the class of bosons. As with other elementary particles, photons are best explained by quantum mechanics and exhibit wave–particle duality, their behavior featuring properties of both waves and particles. The modern photon concept originated during the first two decades of the 20th century with the work of Albert Einstein, who built upon the research of Max Planck. While trying to explain how matter and electromagnetic radiation could be in thermal equilibrium with one another, Planck proposed that the energy stored within a material object should be regarded as composed of an integer number of discrete, equal-sized parts. To explain the photoelectric effect, Eins ...
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Reaction Mechanism
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of an overall chemical reaction. The detailed steps of a reaction are not observable in most cases. The conjectured mechanism is chosen because it is thermodynamically feasible, and has experimental support in isolated intermediates (see next section) or other quantitative and qualitative characteristics of the reaction. It also describes each reactive intermediate, activated complex, and transition state, and which bonds are broken (and in what order), and which bonds are formed (and in what order). A complete mechanism must also explain the reason for the reactants and catalyst used, the stereochemistry observed in reactants and products, all products formed and the amount of each. The electron or arrow pushing method is often used in i ...
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Norrish Reaction
A Norrish reaction in organic chemistry is a photochemical reaction taking place with ketones and aldehydes. Such reactions are subdivided into Norrish type I reactions and Norrish type II reactions. The reaction is named after Ronald George Wreyford Norrish. While of limited synthetic utility these reactions are important in the photo-oxidation of polymers such as polyolefins, polyesters, certain polycarbonates and polyketones. Type I The Norrish type I reaction is the photochemical cleavage or homolysis of aldehydes and ketones into two free radical intermediates (α-scission). The carbonyl group accepts a photon and is excited to a photochemical singlet state. Through intersystem crossing the triplet state can be obtained. On cleavage of the α-carbon bond from either state, two radical fragments are obtained. The size and nature of these fragments depends upon the stability of the generated radicals; for instance, the cleavage of 2-butanone largely yields ethyl radicals in ...
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