Fluorine, isotope

Fluorination, 30 293-294 catalysis, early development, 39 332-334 Fluorine isotope, NMR properties, 33 213, 274 p-Fluoronitrobenzene, 42 168, 171 Fluorotetrasilicic mica... 

The artificial radioactive fluorine isotope F-18 emits positrons (positive electrons) that, when injected into the body, interact with regular negative electrons, and they annihilate... 

Natural fluorine consists entirely of the isotope F and fluorine isotope effects (F KIE) are expected to be small. They were measured for the first time in 1993 [45] in the SNAr reaction of i F/ F fluorodinitrobenzenes with piperidine (Scheme 2). Their value (1.0262 0.0007) [45, 60] suggests a substantial C-F bond breaking in the rate-limiting step of the reaction. 

The labeling of complex compounds can also be achieved by attaching small units, already containing the positron-emitting fluorine isotope, to the main molecular skeleton. Bifunctional fluoroalkanes 18F(CH2) X (n = 1-3, X =Br, OMs, OTs) could be prepared in > 90% radiochemical yield within 10 min. These compounds, especially the tosylates, were then reacted with phenols to give the corresponding [18F]fluoroethers390. Such a reaction... 

Synthetic derivatives and analogs of prenyl diphosphates have historically played a key role in defining key featnres of the mechanism of enzymes that ntilize these key intermediates in the isoprenoid pathway. This has also been the case with the investigation of the protein prenyl-transferases. A brief introduction to the protein prenyltransferase enzymes is given along with outlines on the previous use of prenyl diphosphate tools and key aspects of their synthesis. The development of prenyl diphosphate-based FTase inhibitors is described. The use of prenyl diphosphate derivatives as mechanistic and structural probes is next discussed. In particular, the use of fluorinated, isotopically labeled, and photoaffinity derivatives is presented. An overview of the extensive work on the determination of FTase isoprenoid substrate specificity is then given, and the chapter concludes with a section on the development of prenyl diphosphate tools for proteomic studies. 

Most of the stmctural parameters in this review were derived from electron diffraction data. Clearly, precise comparisons of stmctures should be made on the basis of the same measure of intemuclear distances. Because of the absence of stable fluorine isotopes... 

Write isotopic symbols of the form zX for each isotope. (a) the oxygen isotope with 8 neutrons (b) the fluorine isotope with 10 neutrons (c) the sodium isotope with 12 neutrons (d) the aluminum isotope with 14 neutrons 88. Write isotopic symbols of the form X-A (for example, C-13) for each isotope. (a) the iodine isotope with 74 neutrons (b) the phosphorus isotope with 16 neutrons (c) the uranium isotope with 234 neutrons (d) the argon isotope with 22 neutrons... 

The double-isotopic fractionation method was employed in this study. This procedure consists of the use of deuterium substitution to selectively slow down the rate of one step in a reaction and observing the changes in a second kinetic isotope effect. In this study flie aim is to obtain information from the secondary D KIE at C4 and the fluorine isotope effects, respectively. For that reason, substrates on which the deuterium has been placed at C3 to slow down the step in which the C3-H bond is being broken, have been employed. Then, the extra labels were deuterium at C4 (compound 4) and labeled fluorine (compound 6) (atoms colored red in Fig. 37.1). Compounds 3 and 4 were used to determine the effect of the deuterium at C3 on the secondary D KIE values at C4 (k lk ) (Fig. 37.1). Similarly, compounds 5 and 6 were used to study the influence of the deuterium label at C3 on the leaving group F KIEs... 

We also developed a number of other useful new fluorinating reagents. They ineluded a convenient in situ form of sulfur tetrafluoride in pyridinium polyhydrogen fluoride, selenium tetrafluoride, and ey-anurie fluoride. We introdueed uranium hexafluoride (UFg), depleted from the U-235 isotope, which is an abundant by-product of enrichment plants, as an effective fluorinating agent. 

Before sample preparation, surrogate compounds must be added to the matrix. These are used to evaluate the efficiency of recovery of sample for any analytical method. Surrogate standards are often brominated, fluorinated, or isotopically labeled compounds that are not expected to be present in environmental media. If the surrogates are detected by GC/MS within the specified range, it is... 

The upper part of the figure illustrates why the small difference in mass between an ion and its neutral molecule is ignored for the purposes of mass spectrometry. In mass measurement, has been assigned arbitrarily to have a mass of 12.00000, All other atomic masses are referred to this standard. In the lower part of the figure, there is a small selection of elements with their naturally occurring isotopes and their natural abundances. At one extreme, xenon has nine naturally occurring isotopes, whereas, at the other, some elements such as fluorine have only one. 

For any one element, the abundances (relative amounts) of isotopes can be described in percentage terms. Thus, fluorine is monoisotopic viz., it contains only nuclei of atomic mass 19, and phosphorus has 100% abundance of atoms with atomic mass 31. For carbon, the first two isotopes occur in the proportions of 98.882 to 1.108. 

Another impetus to expansion of this field was the advent of World War 11 and the development of the atomic bomb. The desired isotope of uranium, in the form of UF was prepared by a gaseous diffusion separation process of the mixed isotopes (see Fluorine). UF is extremely reactive and required contact with inert organic materials as process seals and greases. The wartime Manhattan Project successfully developed a family of stable materials for UF service. These early materials later evolved into the current fluorochemical and fluoropolymer materials industry. A detailed description of the fluorine research performed on the Manhattan Project has been pubUshed (2). 

Uranium hexafluoride [7783-81-5], UF, is an extremely corrosive, colorless, crystalline soHd, which sublimes with ease at room temperature and atmospheric pressure. The complex can be obtained by multiple routes, ie, fluorination of UF [10049-14-6] with F2, oxidation of UF with O2, or fluorination of UO [1344-58-7] by F2. The hexafluoride is monomeric in nature having an octahedral geometry. UF is soluble in H2O, CCl and other chlorinated hydrocarbons, is insoluble in CS2, and decomposes in alcohols and ethers. The importance of UF in isotopic enrichment and the subsequent apphcations of uranium metal cannot be overstated. The U.S. government has approximately 500,000 t of UF stockpiled for enrichment or quick conversion into nuclear weapons had the need arisen (57). With the change in pohtical tides and the downsizing of the nation s nuclear arsenal, debates over releasing the stockpiles for use in the production of fuel for civiUan nuclear reactors continue. 

The measurements of concentration gradients at surfaces or in multilayer specimens by neutron reflectivity requires contrast in the reflectivity fiDr the neutrons. Under most circumstances this means that one of the components must be labeled. Normally this is done is by isotopic substitution of protons with deuterons. This means that reflectivity studies are usually performed on model systems that are designed to behave identically to systems of more practical interest. In a few cases, however (for organic compounds containing fluorine, for example) sufficient contrast is present without labeling. 

F is the only isotope of fluorine that occurs naturally, and it has a nuclear spin of j. 

Abundances of lUPAC (the International Union of Pure and Applied Chemistry). Their most recent recommendations are tabulated on the inside front fly sheet. From this it is clear that there is still a wide variation in the reliability of the data. The most accurately quoted value is that for fluorine which is known to better than I part in 38 million the least accurate is for boron (1 part in 1500, i.e. 7 parts in [O ). Apart from boron all values are reliable to better than 5 parts in [O and the majority arc reliable to better than I part in 10. For some elements (such as boron) the rather large uncertainty arises not because of experimental error, since the use of mass-spcctrometric measurements has yielded results of very high precision, but because the natural variation in the relative abundance of the 2 isotopes °B and "B results in a range of values of at least 0.003 about the quoted value of 10.811. By contrast, there is no known variation in isotopic abundances for elements such as selenium and osmium, but calibrated mass-spcctrometric data are not available, and the existence of 6 and 7 stable isotopes respectively for these elements makes high precision difficult to obtain they are thus prime candidates for improvement. 

As it happens, naturally occurring fluorine consists of a single isotope, ijF. It ibllows that the atomic mass of the element fluorine must be the same as that of F-19,19.00 amu. The situation with most elements is more complex, because they occur in nature as a mixture of two or more isotopes. To determine the atomic mass of such an element, it is necessary to know not only the masses of the individual isotopes but also their atom percents (isotopic abundances) in nature. 

Intense molecular ions are observed in the mass spectra of fluorinated benzene, ethyl benzene, toluene, and xylene. Most fluorinated aromatics lose 19 Daltons from the molecular ion. and some lose 50 Daltons (e.g., CF2). The chlorofluoroaromatics can easily be identified by examining the isotope ratios in the vicinity of the molecular ion. 

A few elements, among them fluorine and phosphoras, occur naturally with just one isotope, but most elements are isotopic mixtures. For example, element number 22 is titanium (Ti), a light and strong metal used in Jet engines and in artificial human Joints. There are five naturally occurring isotopes of Ti. Each one has 22 protons in its nuclei, but the number of neutrons varies from 24 to 28. In a chemical reaction, all isotopes of an element behave nearly identically. This means that the isotopic composition of an element remains essentially constant. The isotopic composition of Ti (number percentages) is... 

A — Z N. Because protons and neutrons each have molar mass near 1 g/mol, A is always close to the numerical value of the molar mass of that isotope. For example, fluorine has a molar mass of 18.998 g/mol and A — 19. A particular nuclide can be described by its elemental symbol, X, preceded by the value of A as a... 

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