Cleave

Hydrolases. Enzymes catalysing the hydrolytic cleavage ofC —O, C —N and C —C bonds. The systematic name always includes hydrolase but the recommended name is often formed by the addition of ase to the substrate. Examples are esterases, glucosidases, peptidases, proteinases, phospholipases. Other bonds may be cleaved besides those cited, e.g. during the action of sulphatases and phosphatases. 

Lyases. These enzymes cleave C-C, C-0, C-N and other bonds by elimination leaving double bonds or conversely add groups to double bonds. This group includes decarboxylases, hydratases, dehydratases and some carboxylases. 

C. Excreted in the urine in the rare hereditary disease alkaptonuria. Homogentisic acid is easily oxidized in the air to dark-coloured polymeric products, so that urine from patients with alkaptonuria turns gradually black. It is formed from tyrosine and is an intermediate in tyrosine breakdown in the body. Alkaptonuria is due to the absence of the liver enzyme which cleaves the aromatic ring. 

A major advance in force measurement was the development by Tabor, Win-terton and Israelachvili of a surface force apparatus (SFA) involving crossed cylinders coated with molecularly smooth cleaved mica sheets [11, 28]. A current version of an apparatus is shown in Fig. VI-4 from Ref. 29. The separation between surfaces is measured interferometrically to a precision of 0.1 nm the surfaces are driven together with piezoelectric transducers. The combination of a stiff double-cantilever spring with one of a number of measuring leaf springs provides force resolution down to 10 dyn (10 N). Since its development, several groups have used the SFA to measure the retarded and unretarded dispersion forces, electrostatic repulsions in a variety of electrolytes, structural and solvation forces (see below), and numerous studies of polymeric and biological systems. 

A direct measurement of surface tension is sometimes possible from the work of cleaving a crystal. Mica, in particular, has such a well-defined cleavage plane that it can be split into large sheets of fractional millimeter thickness. Orowan... 

Enzymes are important catalysts in biological organisms and are of increasing use in detergents and sensors. It is of interest to understand not only their adsorption characteristics but also their catalytic activity on the surface. The interplay between adsorption and deactivation has been clearly illustrated [119] as has the ability of a protein to cleave a surface-bound substrate [120]. 

Once a sample is properly oriented and polished, it is placed into a UHV chamber for the final preparation steps. Samples are processed in situ by a variety of methods in order to produce an atomically clean and flat surface. Ion bombardment and aimealing (IBA) is the most conunon method used. Other methods include cleaving and film growth. 

Certain materials, most notably semiconductors, can be mechanically cleaved along a low-mdex crystal plane in situ in a UFIV chamber to produce an ordered surface without contamination. This is done using a sharp blade to slice tire sample along its preferred cleavage direction. For example. Si cleaves along the (111) plane, while III-V semiconductors cleave along the (110) plane. Note that the atomic structure of a cleaved surface is not necessarily the same as that of the same crystal face following treatment by IBA. 

Wliile the earliest TR-CIDNP work focused on radical pairs, biradicals soon became a focus of study. Biradicals are of interest because the exchange interaction between the unpaired electrons is present tliroiighoiit the biradical lifetime and, consequently, the spin physics and chemical reactivity of biradicals are markedly different from radical pairs. Work by Morozova et al [28] on polymethylene biradicals is a fiirther example of how this method can be used to separate net and multiplet effects based on time scale [28]. Figure Bl.16.11 shows how the cyclic precursor, 2,12-dihydroxy-2,12-dimethylcyclododecanone, cleaves upon 308 mn irradiation to fonn an acyl-ketyl biradical, which will be referred to as the primary biradical since it is fonned directly from the cyclic precursor. The acyl-ketyl primary biradical decarbonylates rapidly k Q > 5 x... 

The sample preparation of these mica sheets is a delicate process that requires some experience and often takes 1-2 days prior to an SFA experiment. Tln-ough successive cleaving, one has to prepare 1-5 p.m thick and imifonn sheets of mica. Mica is a natural material that is available m different qualities [44]. 

Each newly cleaved mica surface is very clean. Flowever, it is known that mica has a strong tendency to spontaneously adsorb particles [45] or organic contaminants [46], which may affect subsequent measurements. The mica sheets are cut into 10 nun x 10 nun sized samples using a hot platinum wire, then laid down onto a thick and clean 100 nun x 100 nun mica backing sheet for protection. On the backing sheet, the mica samples can be transferred into a vacuum chamber for themial evaporation of typically 50-55 mn thick silver mirrors. 

In order to understand the tendency to fomi a dipole layer at the surface, imagine a solid that has been cleaved to expose a surface. If the truncated electron distribution originally present within the sample does not relax, this produces a steplike change in the electron density at the newly created surface (figme B1.26.19(A)). 

Figure C2.18.4. Upper panel shows the 2p photoemission spectmm of the Si(l 11)-(2 x ]) cleaved surface after exposure to approximately 50 L of XeF2. The lower panel shows the 2p 2 component of the spectmm after background subtraction. In addition to the unshifted Si(2p2/2), there are tliree chemically shifted satellites...

Zigmond, 1988). The ATP-hydrolysis that accompanies actin polymerization, ATP —> ADP + Pj, and the subsequent release of the cleaved phosphate (Pj) are believed to act as a clock (Pollard et ah, 1992 Allen et ah, 1996), altering in a time-dependent manner the mechanical properties of the filament and its propensity to depolymerize. Molecular dynamics simulations suggested a so-called back door mechanism for the hydrolysis reaction ATP ADP - - Pj in which ATP enters the actin from one side, ADP leaves from the same side, but Pj leaves from the opposite side, the back door (Wriggers and Schulten, 1997b). This hypothesis can explain the effect of the toxin phalloidin which blocks the exit of the putative back door pathway and, thereby, delays Pi release as observed experimentally (Dancker and Hess, 1990). 

On this basis Hendrickson classified organic reactions. A distinction is made between refiinctionalization reactions and skeletal alteration reactions. Refiinctiona-lizations in almost all cases have no more than four carbon atoms in the reaction center. Construction or fragmentation reactions have no more than three carbon atoms in each joining or cleaving part of the molecule. Thus, these parts are treated... 

The independent preparation of potassium phthabmide (from a solution of phthalimide in absolute ethanol and potassium hydroxide in 75 per cent, ethanol) may be avoided in many cases by boiling phthalimide with the halide in the presence of anhydrous potassium carbonate. The N-substituted phthalimide (I) is frequently cleav with difficulty this is often facilitated by reaction with hydrazine hydrate to give an intermediate product, which is easily decomposed by hydrochloric acid to 3deld the insoluble hydrazide of phthaUc acid (II) and the primary amine (III) ... 

The mechanism of the Fries reaction is not known with certainty. One mechanism regards it as a true intramolecular rearrangement in which the acyl group migrates directly from the oxygen atom to the carbon atoms of the ring. Another scheme postulates that the ester is cleaved by the reagent... 

Cyclop entylidene are slightly easier to cleave than acetonides... 

Stable to base cleaved with mild acid... 

Cleaved with mild base such as piperidine, morpholine or dicyclohexylamine... 

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