Optical in nature

Observation of absorption bands due to LO phonons in RAIR spectra of thin, silica-like films deposited onto reflecting substrates demonstrates an important difference between RAIR and transmission spectra. Berreman has shown that absorption bands related to transverse optical (TO) phonons are observed in transmission infrared spectra of thin films obtained at normal incidence [17]. However, bands related to LO phonons are observed in transmission spectra of the same films obtained at non-normal incidence and in RAIR spectra. Thus, it is possible for RAIR and transmission spectra of thin films of some materials to appear very different for reasons that are purely optical in nature. For example, when the transmission infrared spectrum of a thin, silica-like film on a KBr disc was obtained at normal incidence, bands due to TO phonons were observed near 1060,790,and450cm [18]. 

In its disciplinary development at the end of the nineteenth century, physical chemistry served as a bridge, not a wedge, between the mathematical abstractions of theoretical physics and the metaphorical descriptions of organic chemistry. Not only through novel theories but also through control of new instrumentation, much of it electrical and optical in nature, physical chemistry was to revitalize and transform techniques in the chemical laboratory and theories of chemical explanation. Notably for our concerns, speculations about reaction mechanisms in hydrocarbon chemistry were to begin to proliferate in the early 1900s. 

A Thermo-Systems (TSI) Laser-Doppler Anemometer was used to measure the resulting vortex shedding frequencies. This was accomplished by measuring the velocity fluctuations in the direction of flow at some distance downstream from the cylinders. This type of measurements, being inherently optical in nature, did not disturb the flow field and was not influenced by the presence of the polymer. 

The sensor signal is primarily optical in nature and consequently insufficient to block electrical interference from the environment. Such interference may provoke serious problems for electrochemical sensors. 

Falk, D.S., D.R. Brill and D.G. Stork, 1986, Seeing the Light. Optics in nature, photography, vision, and holography (Wiley, New York). 

The element is not found free in nature, but occurs as orthoboric acid usually found in certain volcanic spring waters and as borates in boron and colemantie. Ulexite, another boron mineral, is interesting as it is nature s own version of "fiber optics."... 

The forces which bring about adsorption always include dispersion forces, which are attractive, together with short-range repulsive forces. In addition, there will be electrostatic (coulombic) forces if either the solid or the gas is polar in nature. Dispersion forces derive their name from the close connection between their origin and the cause of optical dispersion. First... 

Synthetic utility of stereoselective alkylations in natural product chemistry is exemplified by the preparation of optically active 2-arylglycine esters (38). Chirally specific a-amino acids with methoxyaryl groups attached to the a-carbon were prepared by reaction of the dimethyl ether of a chiral bis-lactam derivative with methoxy arenes. Using SnCl as the Lewis acid, enantioselectivities ranging from 65 to 95% were obtained. 

Many cycHc ketones occur in natural oils. Jasmone [488-10-8] (3-meth5l-2-(2-pentyl)-2-cyclopenten-l-one) (4) is an odoriferous component of the oil obtained from jasmine flowers. /-Menthone [14073-97-3] (5) is the most frequently occurring of four optically active isomers, and is a colorless Hquid with a minty odor obtained from Mentha species of plants. Muscone [541-91-3] (6) and civetone [542-46-1] (7) are expensive animal products. 

Gitronellol Manufacture. CitroneUol is found widely in nature and in both optically isomeric forms. Prior to the development of synthetic citroneUol, this alcohol was obtained from certain oils of the Kosaceae family or by hydrogenation of citroneUal isolated from citroneUa oil. CitroneUol has a floral odor resembling that of roses. 

Optical absorption measurements give band-gap data for cubic sihcon carbide as 2.2 eV and for the a-form as 2.86 eV at 300 K (55). In the region of low absorption coefficients, optical transitions are indirect whereas direct transitions predominate for quantum energies above 6 eV. The electron affinity is about 4 eV. The electronic bonding in sihcon carbide is considered to be predominantiy covalent in nature, but with some ionic character (55). In a Raman scattering study of vahey-orbit transitions in 6H-sihcon carbide, three electron transitions were observed, one for each of the inequivalent nitrogen donor sites in the sihcon carbide lattice (56). The donor ionization energy for the three sites had values of 0.105, 0.140, and 0.143 eV (57). 

Camphene is the only well-recognised terpene which occurs in nature in the solid condition. It occurs, like pinene, in both optically active forms. The constitution of this terpene has been a matter of considerable difference of opinion, and the constitution assigned to it by Semmler based on its similarity to bomylene was thought by many to be finally accepted. Recent researches, however, have clearly established that the formula assigned to it by Wagner is the correct one. 

Allylic alcohols can be converted to epoxy-alcohols with tert-butylhydroperoxide on molecular sieves, or with peroxy acids. Epoxidation of allylic alcohols can also be done with high enantioselectivity. In the Sharpless asymmetric epoxidation,allylic alcohols are converted to optically active epoxides in better than 90% ee, by treatment with r-BuOOH, titanium tetraisopropoxide and optically active diethyl tartrate. The Ti(OCHMe2)4 and diethyl tartrate can be present in catalytic amounts (15-lOmol %) if molecular sieves are present. Polymer-supported catalysts have also been reported. Since both (-t-) and ( —) diethyl tartrate are readily available, and the reaction is stereospecific, either enantiomer of the product can be prepared. The method has been successful for a wide range of primary allylic alcohols, where the double bond is mono-, di-, tri-, and tetrasubstituted. This procedure, in which an optically active catalyst is used to induce asymmetry, has proved to be one of the most important methods of asymmetric synthesis, and has been used to prepare a large number of optically active natural products and other compounds. The mechanism of the Sharpless epoxidation is believed to involve attack on the substrate by a compound formed from the titanium alkoxide and the diethyl tartrate to produce a complex that also contains the substrate and the r-BuOOH. ... 

In the skeleton of many chelating diphosphines, the phosphorus atoms bear two aryl substituents, not least because the traditional route to this class of compounds involves the nucleophilic substitution with alkali metal diarylphosphides of enantiopure ditosylates derived from optically active natural precursors, approach which is inapplicable to the preparation of P-alkylated analogs. The correct orientation of these aryl substituents in the coordination sphere has been identified as a stereo chemically important feature contributing to the recognition ability of the metal complex [11,18-20]. 

Point defects were mentioned in a prior chapter. We now need to determine how they aiffect the structure auid chemical reactivity of the solid state. We will begin by identifying the various defects which can arise in solids and later will show how they can be manipulated to obtain desirable properties not found in naturally formed solids. Since we have already defined solids as either homogeneous and heterogeneous, let us look first at the homogeneous t5 e of solid. We will first restrict our discussion to solids which are stoichiometric, and later will examine solids which can be classified as "non-stoichiometric", or having an excess of one or another of one of the building blocks of the solid. These occur in semi-conductors as well as other types of electronically or optically active solids. 

The Sonogashira reaction is a transition metal-catalyzed coupling reaction which is widely used for the preparation of alkyl-, aryl- and diaryl-substituted acetylenes (Table 4.7) [120]. This reaction is a key step in natural product synthesis and is also applied in optical and electronic applications. Sonogashira reactions involve the use of an organic solvent with a stoichiometric portion of a base for capturing the... 

Various phenallcylamines were shown to produce either DOM-like or AMPH-like stimulus effects the structure-activity requirements for these activities are different from the standpoints of aromatic substitution patterns, terminal amine substituents, and optical activity. Thus, it has been possible to formulate two distinct SARs. It should be realized, however, that phenalkylamines need not produce only one of these two types of effects certain phenallcylamines can produce pharmacological effects like neither DOM nor AMPH. Moreover, they can produce effects that are primarily peripheral, not central, in nature (Glennon 1987a). The fact that an agent produced DOM- or AMPH-like effects does not imply that it carmot produce an additional effect conversely, if an agent does not produce either DOM- or AMPH-like stimulus effects, it is not necessarily inactive. 

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