Inhibitor sweetening

This paper discusses three aspects of our extensive but as yet incomplete studies of the reaction oxygen uptake in rigorously purified materials, the effects of added iron complexes, and the influence of a well-known radical capture agent. An interesting feature of the last, anticipated from the work of Rosenwald (19) on inhibitor sweetening, was the large accelerating effect of N,N -di- ec-butyl-p-phenylenediamine on the co-oxidation reaction. 

Rosenwald (19) attributed the acceleration of the reactions involved in inhibitor sweetening to the reaction of an unidentified oxidation product of the amine with thiol to produce mercaptyl radicals. However, the oxidation of neat DSBPD is slow at 20°C. (3.3 X 10"5 mole of 02 per mole of amine per second) and partial pre-oxidation of the DSBPD until 0.26 mole of 0> was absorbed per mole of amine did not enhance the activity of the amine (compare curves B and C in Figure 3). Furthermore, allowing the co-oxidation to proceed for a time before adding the... 

Inhibitor sweetening a treating process to sweeten gasoline of low mercaptan content, using a phenylenediamine type of inhibitor, air, and caustic. 

Phytohemoglobins Lectins or Hemagglutinins Biological Activity of Lectins Proteinase Inhibitors Sweeteners References... 

Oxidation Processes. These processes convert mercaptans into less odoriferous disulfides by such processes as the doctor, copper chloride, hypochlorite, and lead sulfide, processes. Since disulfides harm the lead susceptibility of gasoline and since the need of reduction of mercaptans to doctor sweet (0.0004 per cent) is being questioned, these processes are being gradually abandoned. However, catalysts or inhibitors of the 7>-phenylenediamine type, which in the presence of air cause mercaptans in some caustic-washed gasolines to be converted during a few days into disulfides (so-called inhibitor sweetening), continue to be used because of the cheapness of such a process. Small amounts of... 

Inhibitor sweetening of catalytically cracked gasoline is successful and economical for mercaptan contents up to 0.02 to 0.03 per cent. About 6 lb of inhibitor is required per thousand bbl. The final mercaptan content is usually below 0.0015 weight per cent. 

Two undesirable aspects of FCC naphtha quaUty are that it may contain unacceptably high amounts of foul smelling mercaptans, and that its thermal stabiUty may be too low. Mercaptans are usually found in the light FCC naphtha and may be removed or converted to sulfides and disulfides by a sweetening process such as Merox, developed by UOP. Thermal stabiUty is improved in sweetening processes through removal of cresyUc and naphthenic acids. It may be further improved by clay treating and by addition of oxidation inhibitors such as phenylene diamine. 

Other Uses. Other appHcations for sodium nitrite include the syntheses of saccharin [81-07-2] (see Sweeteners), synthetic caffeine [58-08-2] (22), fluoroaromatics (23), and other pharmaceuticals (qv), pesticides (qv), and organic substances as an inhibitor of polymerization (24) in the production of foam blowing agents (25) in removing H2S from natural gas (26) in textile dyeing (see Textiles) as an analytical reagent and as an antidote for cyanide poisoning (see Cyanides). 

Various strains of oral streptococci produce D-glucosyltransferases which utilize sucrose as a o-glucosyl donor in the production of soluble and insoluble D-glucans. Consequently, it may be expected that some deoxyfluoro derivatives of sucrose function as competitive inhibitors for the dextransu-crases of tooth bacteria, thus preventing decay, or at least may be used as active-site probes for the enzymes. Another aim of these researches is to find non-metabolizable sweeteners. 

Alicyclic amines are used as pesticides, plasticizers, explosives, inhibitors of metal corrosion and sweetening agents as well as having uses in the pharmaceuticals industry. Aniline hydrogenation has been studied in the literature with the main reaction products cyclohexylamine, dicyclohexylamine, A-phenylcyclohexylamine, diphenylamine, ammonia, benzene, cyclohexane, cyclohexanol and cyclohexanone [1-9], The products formed depend on the catalyst used, reaction temperature, solvent and whether the reaction is performed in gas or liquid phase. For example high temperature, gas-phase aniline hydrogenation over Rh/Al203 produced cyclohexylamine and dicyclohexylamine as the main products [1],... 

That derivatization may increase rather than decrease peptidase-catalyzed degradation is illustrated with aspartame (6.79, R = MeO), the C-terminal methyl ester of the dipeptide Asp-Phe. The metabolism of this artificial sweetener was compared to that of the underivatized dipeptide (6.79, R = H) and of the corresponding amide Asp-Phe-NH2 (6.79, R = NH2) in microvillar membranes obtained from human duodenum, jejunum, and ileum [189]. The activities monitored were clearly those of peptidases as shown by the effects of inhibitors. Whereas the peptide bond in Asp-Phe and Asp-Phe-NH2 was hydrolyzed at a comparable rate, that in aspartame was hydrolyzed approximately twice as fast. This is an interesting and favorable situation, given that aspartame is expected to be degraded once it has elicited its effect in the buccal cavity. 

Rare or unnatural monosaccharides have many useful applications as nonnutritive sweeteners, glycosidase inhibitors and so on. For example, L-glucose and L-fructose are known to be low-calorie sweeteners. In addition, rare or unnatural monosaccharides are potentially useful as chiral building blocks for the synthesis of biologically active compounds. Therefore, these compounds have been important targets for the development of enzymatic synthesis based in the use of DHAP-dependent aldolases alone or in combination with isomerases. Fessner et al. showed that rare ketose-1-phosphates could be reached not only by aldol addition catalyzed by DHAP-dependent aldolases, but by enzymatic isomerization/ phosphorylation of aldoses [35]. Thus, for example, L-fructose can be prepared... 

Uses/Sources. Production of rubber-processing chemicals corrosion inhibitor in boiler feed water production of insecticides, plasticizers, and dry cleaning soaps a metabolite of the sweetener cyclamate... 

Some chemical additives such as corrosion inhibitors, wax crystal modifiers, detergents, and demulsifiers provide performance which is difficult to duplicate through refining without adversely affecting some other fuel property. Other additives such as metal chelators, fuel sweeteners, biocides, lubricity improvers, foam control agents and combustion enhancers can also be used to solve fuel performance problems. 

Since HtS dissolved in water is very corrosive to carbon 4 steel, a comprehensive corrosion-control program is being conducted. In the field, each well is treated once per month by displacing inhibitor down to the perfora-. tions with stock tank oil. Corrosion coupons in the flow-lines are inspected every 6 months Little corrosion has been detected in the field. In the plants, corrosion in-hibitor is added daily to the gas-sweetening solvent, the salt water system, and the stabilizer overhead. Inhibitor is -Jj also added to bulk chemicals as received. Numerous corrosion coupons and probes are installed in each facility and are pulled for inspection every 1 to 3 months Corrosion rates have been low (less than I mil/year) asY result of the inhibitor injection program. 

The introduction of retro-, retro-inverso-, and PMRI-peptides with free and blocked C-and N-termini has been successful in numerous biological systems such as neurotransmitters, inhibitors of proteases and protein kinases, sweeteners, antimicrobial peptides, hormones, adhesion molecules, antigenic epitopes, immuno-modulators, and immunological probes. Table 1 provides an exhaustive list of retro-, retro-inverso-, PMRI-, and end-group-modified re/ro-mvmo-pseudopeptides derived from bioactive peptides. 

In the mid to late 1980s, many research groups focused on methods and processes to prepare L-phenylalanine (Chapter 3). This was a direct result of the demand for the synthetic, artificial sweetener aspartame. One of the many routes studied was the use of phenylalanine dH (Scheme 19.4, R = C6H5CH2) with phenylpyruvate (PPA) as substrate.57-58 This enzyme from Bacillus sphaericus shows a broad substrate specificity and, thus, has been used to prepare a number of derivatives of L-phenylalanine.59 A phenylalanine dH isolated from a Rhodococcus strain M4 has been used to make L-homophenylalanine (.S )-2-amino-4-pheny I butanoic acid], a key, chiral component in many angiotensin-converting enzyme (ACE) inhibitors.40 More recently, that same phenylalanine dH has been used to synthesize a number of other unnatural amino acids (UAAs) that do not contain an aromatic sidechain.43... 

Uses Cyclohexylamine is a strong inflammable liquid with a fish-like odor. It has many applications in both household and industrial processing (e.g., a corrosion inhibitor in water boilers, the synthesis of pesticides, dry-cleaning soaps, the manufacture of plasticizers, textile chemicals, cyclamates (artificial sweeteners), dyestuffs).41,49... 

Cyclohexylamines Corrosion inhibitors, catalysts, antibiotics, herbicides, cycla-mate sweeteners in Asia... 

Interestingly, the human TAS1R2/TAS1R3, but not its mouse counterpart, are sensitive to the sweet proteins monellin, thaumatin, and brazzein, and to the artificial sweeteners neo-tame, cyclamate, and aspartame (9-11). This difference provides a molecular explanation for the previous observation that these compounds are sweet for humans but not attractive to rodents (9). The species difference also applies to the inhibitor lactisole that blocks the sweet taste in humans but not in rats, and only inhibits the response of human TAS1R2/TAS1R3 to sweet stimuli (9). 

A number of synthetic peptides are significant commercial products, ranging from the sweet dipeptide aspartame (L-aspartyl-L-phenylalanine methyl ester) to clinically used hormones such as insulin and oxytocin. L-Aspartyl-L-phenylalanine methyl ester (3 Scheme 2) is the methyl ester of the C-terminal dipeptide of gastrin. It was found accidently during the synthesis of gastrin that this synthetic sweetener is about 200 times as sweet as sucrose.f This pleasant sweetness without a bitter aftertaste was the reason that L-aspartyl-L-phenylalanine methyl ester was approved in many countries as a food additive, receiving much attention as a low-calorie sweetener. L-Aspartyl-L-phenylalanine methyl ester can be prepared by various chemical routes and the first enzymatic procedure of commercial interest was described by Isowa et al.h l In the industrial process,L-Asp and DL-Phe were chosen as inexpensive raw materials. L-Asp is available very inexpensively, whereas L-Phe is more expensive than DL-Phe. Z-D-Asp acts as a competitive inhibitor, while D-Phe-OMe... 

Besides the naturally occurring saccharides and polyols, there are a number of plant-derived highly sweet compounds, which are mostly terpenoids, flavonoids, and proteins [16-18]. Several of these sweet substances are used commercially as sucrose substitutes, as will be described in the next section. In addition, a number of plant substituents are known to mediate the sweet-taste response, either by inducing or inhibiting the perception of sweemess [19]. Thus far, all of the known natural product sweet-tasting substances and sweetness modifiers have been obtained from green plants [16-19]. In the remaining sections of this chapter, plant-derived sweet compounds with commercial use will be described, followed by a section on recent theories on the sweet taste phenomenon, and then individual descriptions of potent sweeteners, sweetness inducers, and sweetness inhibitors from plants will be presented in turn. The literature has been surveyed for this chapter until the end of 1999. 

The NCA/NTA technology has found application in the synthesis of fragments of ribonuclease A, as well as in the large scale synthesis of ACE inhibitor precursors of enalapriP - and the artificial sweetener aspartam. ... 

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