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CIDNP
CIDNP (chemically induced dynamic nuclear polarization), often pronounced like "kidnip", is a nuclear magnetic resonance (NMR) technique that is used to study chemical reactions that involve radicals. It detects the non-Boltzmann (non-thermal) nuclear spin state distribution produced in these reactions as enhanced absorption or emission signals. CIDNP was discovered in 1967 by Bargon and Fischer, and, independently, by Ward and Lawler. Early theories were based on dynamic nuclear polarisation (hence the name) using the Overhauser Effect. The subsequent experiments, however, have found that in many cases DNP fails to explain CIDNP polarization phase. In 1969 an alternative explanation which relies on the nuclear spins affecting the probability of a radical pair recombining or separating. It is related to chemically induced dynamic electron polarization (CIDEP) insofar as the radical-pair mechanism explains both phenomena. Concept and experimental set-up The effect is detected by ...
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Overhauser Effect
Dynamic nuclear polarization (DNP) results from transferring spin polarization from electrons to nuclei, thereby aligning the nuclear spins to the extent that electron spins are aligned. Note that the alignment of electron spins at a given magnetic field and temperature is described by the Boltzmann distribution under the thermal equilibrium. It is also possible that those electrons are aligned to a higher degree of order by other preparations of electron spin order such as: chemical reactions (leading to Chemical-Induced DNP, CIDNP), optical pumping and spin injection. DNP is considered one of several techniques for hyperpolarization. DNP can also be induced using unpaired electrons produced by radiation damage in solids. When electron spin polarization deviates from its thermal equilibrium value, polarization transfers between electrons and nuclei can occur spontaneously through electron-nuclear cross relaxation and/or spin-state mixing among electrons and nuclei. For example, the ...
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Nuclear Magnetic Resonance
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of the nuclei, which depends on the strength of the static magnetic field, the chemical environment, and the magnetic properties of the isotope involved; in practical applications with static magnetic fields up to ca. 20  tesla, the frequency is similar to VHF and UHF television broadcasts (60–1000 MHz). NMR results from specific magnetic properties of certain atomic nuclei. Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and study molecular physics and crystals as well as non-crystalline materials. ...
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Fluorescence
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, than the absorbed radiation. A perceptible example of fluorescence occurs when the absorbed radiation is in the ultraviolet region of the electromagnetic spectrum (invisible to the human eye), while the emitted light is in the visible region; this gives the fluorescent substance a distinct color that can only be seen when the substance has been exposed to UV light. Fluorescent materials cease to glow nearly immediately when the radiation source stops, unlike phosphorescent materials, which continue to emit light for some time after. Fluorescence has many practical applications, including mineralogy, gemology, medicine, chemical sensors (fluorescence spectroscopy), fluorescent labelling, dyes, biological detectors, cosmic-ray detection, vacu ...
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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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Spin Polarization
Spin polarization is the degree to which the spin, i.e., the intrinsic angular momentum of elementary particles, is aligned with a given direction. This property may pertain to the spin, hence to the magnetic moment, of conduction electrons in ferromagnetic metals, such as iron, giving rise to spin-polarized currents. It may refer to (static) spin waves, preferential correlation of spin orientation with ordered lattices (semiconductors or insulators). It may also pertain to beams of particles, produced for particular aims, such as polarized neutron scattering or muon spin spectroscopy. Spin polarization of electrons or of nuclei, often called simply magnetization, is also produced by the application of a magnetic field. Curie law is used to produce an induction signal in Electron spin resonance (ESR or EPR) and in Nuclear magnetic resonance (NMR). Spin polarization is also important for spintronics, a branch of electronics. Magnetic semiconductors are being researched as possib ...
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Deprotonation
Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.edu/hjakubowski/classes/ch331/protstructure/PS_2A3_AA_Charges.html, accessed 12/2/2020 The species formed is the conjugate base of that acid. The complementary process, when a proton is added (transferred) to a Brønsted–Lowry base, is protonation (or hydronation). The species formed is the conjugate acid of that base. A species that can either accept or donate a proton is referred to as amphiprotic. An example is the H2O (water) molecule, which can gain a proton to form the hydronium ion, H3O+, or lose a proton, leaving the hydroxide ion, OH−. The relative ability of a molecule to give up a proton is measured by its p''K''a value. A low p''K''a value indicates that the compound is acidic and will easily give up its proton to a base ...
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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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Electron Transfer Reaction
The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought to be elementary particles because they have no known components or substructure. The electron's Invariant mass, mass is approximately Proton-to-electron mass ratio, 1/1836 that of the proton. Quantum mechanics, Quantum mechanical properties of the electron include an intrinsic angular momentum (spin (physics), spin) of a half-integer value, expressed in units of the reduced Planck constant, . Being fermions, no two electrons can occupy the same quantum state, in accordance with the Pauli exclusion principle. Like all elementary particles, electrons exhibit properties of wave-particle duality, both particles and waves: They can collide with other particles and can be electron diffraction, diffracted like light. The #Quantum properties, wave ...
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Diffusion-controlled Reaction
Diffusion-controlled (or diffusion-limited) reactions are reactions in which the reaction rate is equal to the rate of transport of the reactants through the reaction medium (usually a solution). The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency. Diffusion control is rare in the gas phase, where rates of diffusion of molecules are generally very high. Diffusion control is more likely in solution where diffusion of reactants is slower due to the greater number of collisions with solvent molecules. Reactions where the activ ...
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Polycyclic Aromatic Hydrocarbon
A polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings. The simplest representative is naphthalene, having two aromatic rings and the three-ring compounds anthracene and phenanthrene. PAHs are uncharged, non-polar and planar. Many are colorless. Many of them are found in coal and in oil deposits, and are also produced by the combustion of organic matter—for example, in engines and incinerators or when biomass burns in forest fires. Polycyclic aromatic hydrocarbons are discussed as possible starting materials for abiotic syntheses of materials required by the earliest forms of life. Nomenclature and structure The terms polyaromatic hydrocarbon or polynuclear aromatic hydrocarbon are also used for this concept. By definition, polycyclic aromatic hydrocarbons have multiple rings, precluding benzene from being considered a PAH. Some sources, such as the US EPA and CDC, consider naphthalene to be the simplest PAH. ...
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Phenol
Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it requires careful handling because it can cause chemical burns. Phenol was first extracted from coal tar, but today is produced on a large scale (about 7 billion kg/year) from petroleum-derived feedstocks. It is an important industrial commodity as a precursor to many materials and useful compounds. It is primarily used to synthesize plastics and related materials. Phenol and its chemical derivatives are essential for production of polycarbonates, epoxies, Bakelite, nylon, detergents, herbicides such as phenoxy herbicides, and numerous pharmaceutical drugs. Properties Phenol is an organic compound appreciably soluble in water, with about 84.2 g dissolving in 1000 mL (0.895 M). Homogeneous mixtures of phenol and water at phenol ...
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Ionization Potential
Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule is called an ion. Ionization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules and ions, or through the interaction with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution reactions can result in the formation of ion pairs. Ionization can occur through radioactive decay by the internal conversion process, in which an excited nucleus transfers its energy to one of the inner-shell electrons causing it to be ejected. Uses Everyday examples of gas ionization are such as within a fluorescent lamp or other electrical discharge lamps. It is also used in radiation detectors such as the Geiger-Müller counter or the ionization chamber. The ionizat ...
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