Self catalyst

A recent discovery that RNA will act as a self-catalyst, called a ribozyme, leads to a simple three-step model for self-replication - this might include a surface. In the model (Figure 8.18), the template molecule T is self-complementary and is able to act as an autocatalyst. In the first step, it reversibly binds with its constituents A and B, forming the termolecular complex M. The termolecular complex undergoes irreversible polymerisation and becomes the duplex molecule D. Reversible dissociation of D gives two template molecules T, which can initiate new replication. The model preserves the order of the moieties on the template (the direction of the arrow) and the backbone, which may be on the surface... 

Soai K, Niwa S, Hori H Asymmetric self-catalytic reaction — Self-production of chiral l-(3-pyridyl)alkanols as chiral self-catalysts in the enantioselective addition of dialkylzinc reagents to pyridine-3-carbaldehyde. J Chem Soc Chem Common 1990, (l4) 982-983. 

In the case in which no catalyst is added it is found experimentally that acid groups in the reaction mixture act as self-catalysts. The basic elementary reaction is then... 

The power of optical spectroscopies is that they are often much better developed than their electron-, ion- and atom-based counterparts, and therefore provide results that are easier to interpret. Furtlienuore, photon-based teclmiques are uniquely poised to help in the characterization of liquid-liquid, liquid-solid and even solid-solid interfaces generally inaccessible by other means. There has certainly been a renewed interest in the use of optical spectroscopies for the study of more realistic systems such as catalysts, adsorbates, emulsions, surfactants, self-assembled layers, etc. 

Cerium is a component of misch metal, which is extensively used in the manufacture of pyrophoric alloys for cigarette lighters. While cerium is not radioactive, the impure commercial grade may contain traces of thorium, which is radioactive. The oxide is an important constituent of incandescent gas mantles and is emerging as a hydrocarbon catalyst in self cleaning ovens. In this application it can be incorporated into oven walls to prevent the collection of cooking residues. 

The nitronium ions produced in this way tend to repress the selfdehydration of the nitric acid and therefore the net concentration of nitronium ions is not proportional to the concentration of the catalyst. When sufficient sulphuric acid has been added to make the self-ioniza-tion of nitric acid relatively unimportant, the nitronium ions will be produced predominantly from the above ionization, and the acceleration will follow a linear law. 

Reaction (5.N) describes the nylon salt nylon equilibrium. Reactions (5.0) and (5.P) show proton transfer with water between carboxyl and amine groups. Since proton transfer equilibria are involved, the self-ionization of water, reaction (5.Q), must also be included. Especially in the presence of acidic catalysts, reactions (5.R) and (5.S) are the equilibria of the acid-catalyzed intermediate described in general in reaction (5.G). The main point in including all of these equilibria is to indicate that the precise concentration of A and B... 

Reactions with Aldehydes and Ketones. The base-catalyzed self-addition of acetaldehyde leads to formation of the dimer, acetaldol [107-89-1/, which can be hydrogenated to form 1,3-butanediol [107-88-0] or dehydrated to form crotonaldehyde [4170-30-3]. Crotonaldehyde can also be made directiy by the vapor-phase condensation of acetaldehyde over a catalyst (53). 

Reaction of one mole of acetaldehyde and excess phenol in the presence of a mineral acid catalyst gives l,l-bis(p-hydroxyphenyl)ethane [2081-08-5], acid catalysts, acetaldehyde, and three moles or less of phenol yield soluble resins. Hardenable resins are difficult to produce by alkaline condensation of acetaldehyde and phenol because the acetaldehyde tends to undergo aldol condensation and self-resinification (see Phenolic resins). 

Phenolic Resins. Phenohc resins (qv) are formed by the reaction of phenol [108-95-2] C H O, and formaldehyde [50-00-0] CH2O. If basic conditions and an excess of formaldehyde are used, the result is a resole phenohc resin, which will cure by itself Hberating water. If an acid catalyst and an excess of phenol are used, the result is a novolac phenohc resin, which is not self-curing. Novolac phenohc resins are typically formulated to contain a curing agent which is most often a material known as hexamethylenetetraamine [100-97-0] C H22N4. Phenohc resin adhesives are found in film or solution... 

CaniZZaro Reaction. Both 2- and 4-hydroxybenzaldehydes undergo this self-oxidation—reduction reaction, but much less readily than benzaldehyde the reaction requires metal catalysts such as nickel, cobalt, or silver to yield the corresponding hydroxybenzoic acids and hydroxybenzyl alcohols (47—48). 

Because lactic acid has both hydroxyl and carboxyl functional groups, it undergoes iatramolecular or self-esterificatioa and forms linear polyesters, lactoyUactic acid (4) and higher poly(lactic acid)s, or the cycUc dimer 3,6-dimethyl-/)-dioxane-2,5-dione [95-96-5] (dilactide) (5). Whereas the linear polyesters, lactoyUactic acid and poly(lactic acid)s, are produced under typical condensation conditions such as by removal of water ia the preseace of acidic catalysts, the formation of dilactide with high yield and selectivity requires the use of special catalysts which are primarily weakly basic. The use of tin and ziac oxides and organostaimates and -titanates has been reported (6,21,22). 

Silicon Nitride. SiUcon nitride is manufactured either as a powder as a precursor for the production of hot-pressed parts or as self-bonded, reaction-sintered, siUcon nitride parts. a-SiUcon nitride, used in the manufacture of Si N intended for hot pressing, can be obtained by nitriding Si powder in an atmosphere of H2, N2, and NH. Reaction conditions, eg, temperature, time, and atmosphere, have to be controlled closely. Special additions, such as Fe202 to the precursor material, act as catalysts for the formation of predorninately a-Si N. SiUcon nitride is ball-milled to a very fine powder and is purified by acid leaching. SiUcon nitride can be hot pressed to full density by adding 1—5% MgO. 

Examples include acetaldehyde, CH CHO paraldehyde, (CH CHO) glyoxal, OCH—CHO and furfural. The reaction is usually kept on the acid side to minimize aldol formation. Furfural resins, however, are prepared with alkaline catalysts because furfural self-condenses under acid conditions to form a gel. 

Chemical Hazards. Chemical manufacturers and employees contend with various ha2ards inherent ia productioa of evea commonplace materials. For example, some catalysts used ia the manufacture of polyethylene (see Olefin polymers) ignite when exposed to air or explode if allowed to become too warm the basic ingredient ia fluorocarboa polymers, eg, Tefloa (see Fluorine compounds, organic), can become violently self-reactive if overheated or contaminated with caustic substances (45,46) one of the raw materials for the manufacture of acryflc fibers (see Fibers, acrylic) is the highly toxic hydrogen cyanide (see Cyanides). 

Flame Retardants. Flame retardants are added to nylon to eliminate burning drips and to obtain short self-extinguishing times. Halogenated organics, together with catalysts such as antimony trioxide, are commonly used to give free-radical suppression in the vapor phase, thus inhibiting the combustion process. Some common additives are decabromodiphenyl oxide, brominated polystyrene, and chlorinated... 

Liquid crystal polyesters are made by a different route. Because they are phenoHc esters, they cannot be made by direct ester exchange between a diphenol and a lower dialkyl ester due to unfavorable reactivities. The usual method is the so-called reverse ester exchange or acidolysis reaction (96) where the phenoHc hydroxyl groups are acylated with a lower aHphatic acid anhydride, eg, acetic or propionic anhydride, and the acetate or propionate ester is heated with an aromatic dicarboxyHc acid, sometimes in the presence of a catalyst. The phenoHc polyester forms readily as the volatile lower acid distills from the reaction mixture. Many Hquid crystal polymers are derived formally from hydroxyacids (97,98) and thein acetates readily undergo self-condensation in the melt, stoichiometric balance being automatically obtained. 

The replacement of the hydrogen of the methylo1 compound with an alkyl group renders the compound much more soluble in organic solvents and more stable. This reaction is also cataly2ed by acids and usually carried out in the presence of considerable excess alcohol to suppress the competing self-condensation reaction. After neutrali2ation of the acid catalyst, the excess alcohol may be stripped or left as a solvent for the amino resin. 

On curing, amino resins not only react with the nucleophilic sites (hydroxyl, carboxyl, amide) on the other film formers in the formulation, but also self-condense to some extent. Highly alkylated amino resins have less tendency to self-condense (33,34) and are therefore effective cross-linking agents, but may require the addition of a strong acid catalyst to obtain acceptable cure even at bake temperatures of 120—177°C. 

Other methods also exist for handling the reaction mixture. For instance, self-wiping, twin-screw extmder using an intermeshing has been proposed (271). The advantages claimed include higher saponification temperature (less catalyst), increased water solubiUty (271), and fewer impurities (272). 

Benzoin, [119-53-9] 2-hydroxy-2-phenylacetophenone, CgH CH(OH)COCgH (mp, 133—137°C bp, 343—344°C at 101.3 kPa), is formed by the self-condensation of benzaldehyde in the presence of potassium cyanide. It is used on a small scale as a polymerization catalyst in polyester resin manufacture. 

Benzyl chloride reacts with benzene in the presence of a Lewis acid catalyst to give dipbenylmetbane [101 -81-5]. It undergoes self-condensation to form polymeric oils and soHds (21). With phenol, benzyl chloride produces a mixture of o- andp-her zylpbeno1. 

Aromatic Ring Reactions. In the presence of an iodine catalyst chlorination of benzyl chloride yields a mixture consisting mostly of the ortho and para compounds. With strong Lewis acid catalysts such as ferric chloride, chlorination is accompanied by self-condensation. Nitration of benzyl chloride with nitric acid in acetic anhydride gives an isomeric mixture containing about 33% ortho, 15% meta, and 52% para isomers (27) with benzal chloride, a mixture containing 23% ortho, 34% meta, and 43% para nitrobenzal chlorides is obtained. 

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