Open stability

Onium ions of small and large heterocyclics are usually produced by electrophilic attack on a heteroatom. In three- and four-membered rings nucleophilic attack on an adjacent carbon follows immediately, in most cases, and ring opening stabilizes the molecule. In large rings the onium ion behaves as would its acyclic analog, except where aromaticity or transannular reactions come into play (each with its electronic and steric pre-conditions). A wide diversity of reactions is observed. 

Hb Zurich /363 His—>Arg Heme pocket opened, stability decreased Proximal histidine group... 

Methemo- Hb St. Louis /328 Leu—>Gln Heme pocket opened, stabil-... 

Figure C2.5.10. The figure gives tire foldability index ct of 27-mer lattice chains witli sets containing different number of amino acids. The sets are generated according to scheme described in [27], The set of 20 amino acids is taken as a standard sample. Each sequence witli 20 amino acids is optimized to fulfil tire stability gap [5]. The residues in tire standard samples are substituted witli four different sets containing a smaller number of amino acids [27]. The foldability of tliese substitutions is indicated by tire full circles. The open diamonds correspond to tire sequences witli same composition. However, tire amino acids are chosen from tire reduced representation and tire resultant sequence is optimized using tire stability gap [5].

The general pattern of alkylation of 2-acylaininothiazoles parallels that of 2-aminothia2ole itself (see Section III.l). In neutral medium attack occurs on the ring nitrogen, and in alkaline medium a mixture of N-ring and N-amino alkylation takes place (40, 43, 161. 163). In acidic medium unusual behavior has been reported (477) 2-acetamido-4-substituted thiazoles react with acetic anhydride in the presence of sulfuric acid to yield 2-acetylimino-3-acetyl-4-phenyl-4-thiazolines (255) when R = Ph. but when R4 = Me or H no acetylation occurs (Scheme 151). The explanation rests perhaps in an acid-catalyzed heterocyclization with an acetylation on the open-chain compound (253), this compound being stabilized... 

As with a plasma-arc furnace, various gases and pneumatically conveyed soHds have been added to the various types of a-c open-arc furnaces to decrease alloy loss, to stabilize the arc, and to decrease the noise level, but with mixed commercial success. 

The following mechanisms in corrosion behavior have been affected by implantation and have been reviewed (119) (/) expansion of the passive range of potential, (2) enhancement of resistance to localized breakdown of passive film, (J) formation of amorphous surface alloy to eliminate grain boundaries and stabilize an amorphous passive film, (4) shift open circuit (corrosion) potential into passive range of potential, (5) reduce/eliminate attack at second-phase particles, and (6) inhibit cathodic kinetics. 

Dead-burned dolomite is a specially sintered or double-burned form of dolomitic quicklime which is further stabilized by the addition of iron oxides. Historically, it was used as a refractory for lining steel furnaces, particularly open hearths, but as of this writing is used primarily in making dolomite refractory brick (see Refractories). 

PefractoTy lime is synonymous with dead-burned dolomite, an unreactive dolomitic quicklime, stabilized with iron oxides, that is used primarily for lining refractories of steel furnaces, particularly open hearths. 

Sohd materials, such as gilsonite and asphalt, and partially soluble sulfonated asphalt may also be added to plug small fractures in exposed shale surfaces and thereby limit water entry into the formation (105,124). The asphalts are oxidized or treated to impart partial solubiUty. These materials may be softened by the downhole temperature, causing them to deform and squeeze into small openings exposed to the borehole. Laboratory tests designed to evaluate shale-stabilizing muds have confirmed the beneficial action of these materials (125) (see also Soil STABILIZATION). 

Ca.rdia.c-AssistDevices. The principal cardiac-assist device, the intra-aortic balloon pump (lABP), is used primarily to support patients before or after open-heart surgery, or patients who go into cardiogenic shock. As of the mid-1990s, the lABP was being used more often to stabilize heart attack victims, especially in community hospitals which do not provide open-heart surgery. The procedure consists of a balloon catheter inserted into the aorta which expands and contracts to assist blood flow into the circulatory system and to reduce the heart s workload by about 20%. The disposable balloon is powered by an external pump console. 

Clearly, in the case of (66) two amide tautomers (72) and (73) are possible, but if both hydroxyl protons tautomerize to the nitrogen atoms one amide bond then becomes formally cross-conjugated and its normal resonance stabilization is not developed (c/. 74). Indeed, part of the driving force for the reactions may come from this feature, since once the cycloaddition (of 72 or 73) has occurred the double bond shift results in an intermediate imidic acid which should rapidly tautomerize. In addition, literature precedent suggests that betaines such as (74) may also be present and clearly this opens avenues for alternative mechanistic pathways. 

In aqueous alkaline conditions with chloroacetic acid the pyrido[4,3- f]pyrimidinethione (80) undergoes facile ring opening, attributed to the resonance stabilization of a delocalized covalent hydrate dianion intermediate (81) (82). Pyrido[2,3- f]pyrimidine-4-thiones (and... 

A modified definition of resonance energy has been introduced by Dewar (66T(S8)75, 69JA6321) in which the reference point is the corresponding open-chain polyene. In principle this overcomes the difficulties inherent in comparing observed stability with that of an idealized molecule with pure single and double bonds, as thermochemical data for the reference acyclic polyenes are capable of direct experimental determination. In practice, as the required data were not available, recourse was made to theoretical calculations using a semiempirical SCF-MO method. The pertinent Dewar Resonance Energies are listed in Table 30. 

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