Sulfonic acids, detection

Water satd. butanol containing 2% p-toluene-sulfonic acid Detection As PC3... 

For the separation of aliphatic and aromatic acids, especially from substances of nonionic character, paper electrophoresis can be applied successfully. With a potential drop of lOV/cm and with 2n ammonia or 1 N acetic acid as a buffer, the separation can be carried out in 2 hr. Mono-, di-, and polysulfonated derivatives are also separated, but not isomeric sulfonic acids. Detection is carried out as in paper chromatography. 

Suzuki, N., etal. (1991). Studies on the chemiluminescent detection of active oxygen species 9-acridone-2-sulfonic acid, a specific probe for superoxide. Agric. Biol. Chem. 55 1561-1564. 

The lack of any difference in the rate of isomerization between fluoro-sulfonic acid solutions of 34 which had been thoroughly degassed, and those which were saturated with oxygen, suggests that the reaction does not proceed via a triplet mechanism. In fluorosulfonic acid no unproton-ated acid is detected, ruling out the possibility of n,7r excitation. Thus, there is little doubt in this case that it is the Tr,Tr singlet state which is the reactive species. Experiments carried out with a variety of methyl-substituted protonated cydohexadienones have likewise ruled out the... 

Limits of detection for each of the six soil metabolites in surface water and ground-water were determined by using an estimate of variability for the 0.25 pgL fortifications from samples analyzed along with hundreds of surface water and groundwater sets during the years 1999-2001. During these years, the estimated LODs were below 0.1 ug for acetochlor sulfonic acid, acetochlor oxanilic acid, alachlor oxanilic acid, metolachlor sulfonic acid, and metolachlor oxanilic acid and about 0.1 igL for alachlor sulfonic acid. If the actual concentration of an analyte is at this detection limit or greater, there is at least a 95% chance of detection. 

Seven replicate recoveries of flucarbazone-sodium, sulfonic acid, sulfonamide and NODT from well water fortified af 50 ng L averaged 106,100,89 and 106%, respec-fively. Therefore, the LOQ is 50 ng L for each analyte. The method detection limits for flucarbazone-sodium, sulfonic acid, sulfonamide and NODT, as determined by the United States Environmental Protection Agency (USEPA) recommended technique, are 5, 11, 20 and 19ngL, respectively. 

Only few applications have been reported to determine antioxidants in rubbers or polymers by using electrochemical methods [927,928]. Sawada et al. [929] reported successful separations by coupling the antioxidants with p-diazobenzene sulfonic acid before electrophoresis. Amine AOs were coupled in acetic acid and phenolic AOs in NaOH-ethanol were analysed by CE methods. MEKC separation of the four major food grade antioxidants (PG, BHA, BHT, TBHQ) was completed within 6 min with pmole amount detection using UV absorption [930]. RPLC was not as efficient and required larger sample amounts and longer separation times. 

Desulfurization using purified enzymes Investigations into enzymatic desulfurization as an alternative to microbial desulfurization has revealed several enzymes capable of the initial oxidation of sulfur. A study reported use of laccase with azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator for oxidation of DBT [181]. The rate of this reaction was compared to hydrogen peroxide-based phosphotungstic acid-catalyzed oxidation and the latter was found to be about two orders of magnitude higher. The authors also oxidized diesel oil sulfur to no detectable levels via extraction of the oxidized sulfur compounds from diesel. In Table 9, the enzymes used in oxidation of DBT to DBTO are reported. 

Al-Ghannam et al. [25] described a simple fluorimetric procedure for determination of three pharmaceutical compounds containing thiol groups, including penicillamine. In this method, the drugs are treated with 1,2-naphthoquinone-4-sulfonic acid. The later compound is reduced to l,2-dihydroxynaphthalene-4-sulfonic acid, which is measured fluorimetrically (excitation = 318 nm, emission = 480 nm). The method is sensitive to 0.5 1.5 pg/mL, with a detection limit of 0.05 pg/mL (S/N = 2). 

Gotti et al. [42] reported an analytical study of penicillamine in pharmaceuticals by capillary zone electrophoresis. Dispersions of the drug (0.4 mg/mL for the determination of (/q-penicillaminc in water containing 0.03% of the internal standard, S -met hy I - r-cystei ne, were injected at 5 kPa for 10 seconds into the capillary (48.5 cm x 50 pm i.d., 40 cm to detector). Electrophoresis was carried out at 15 °C and 30 kV, with a pH 2.5 buffer of 50 mM potassium phosphate and detection at 200 rnn. Calibration graphs were linear for 0.2-0.6 pg/mL (detection limit = 90 pM). For a more sensitive determination of penicillamine, or for the separation of its enantiomers, a derivative was prepared. Solutions (0.5 mL, final concentration 20 pg/mL) in 10 mM phosphate buffer (pH 8) were mixed with 1 mL of methanolic 0.015% 1,1 -[ethylidenebis-(sulfonyl)]bis-benzene and, after 2 min, with 0.5 mL of pH 2.5 phosphate buffer. An internal standard (0.03% tryptophan, 0.15 mL) was added and aliquots were injected. With the same pH 2.5 buffer and detection at 220 nm, calibration graphs were linear for 9.3-37.2 pg/mL, with a detection limit of 2.5 pM. For the determination of small amounts of (L)-penicillamine impurity, the final analyte concentration was 75 pg/mL, the pH 2.5 buffer contained 5 mM beta-cyclodextrin and 30 mM (+)-camphor-10-sulfonic acid, with a voltage of 20 kV, and detection at 220 nm. Calibration graphs were linear for 0.5-2% of the toxic (L)-enantiomer, with a detection limit of 0.3%. 

ABTS 2,2,-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) dm dry matter n.d. not detected ORAC oxygen radical absorbance capacity. 

Bhat et al. [199] used complexation with the bis(ethylenediamine) copper (II) cation as the basis of a method for estimating anionic surfactants in fresh estuarine and seawater samples. The complex is extracted into chloroform, and copper is measured spectrophotometrically in the extract using l,2(pyridyl azo)-2-naphthol. Using the same extraction system these workers were able to improve the detection limit of the method to 5 pg/1 (as linear alkyl sulfonic acid) in fresh estuarine and seawater samples. 

This ESI(+) TIC, however, is dominated by strong and broad signals that eluted between 17 and 31 min, neither observable under APCI(+/—) nor ESI(-) conditions. Even under gradient RP-C18 conditions a strong tailing effect was observed while isocratic RP-C18 failed. The information obtained by ESI—LC—MS(+) was that the compounds could be ionised in the form of [M]+ ions at m/z 230, 258 and 286. ESI-LC-MS-MS(+) resulted in product ion spectra which, by means of a MS-MS library, were found to be characteristic for the amphoteric amine oxide surfactants. These compounds not yet observed in household formulations will be presented later on with the RIC of LC separation (cf. Fig. 2.5.11(d)). After identification as amine oxides, the separation and detection of this compound mixture now could be achieved by an isocratic elution using a PLRP-column and methane sulfonic acid and ESI(+) ionisation with the result of sharp signals (RT = 4-6 min) as presented in Fig. 2.5.11(d). 

The pH value also affects the ionization of acidic and basic analytes and their electromigration. Since this migration can be opposite to that of the electroos-motic flow, it may both improve and impair the separation. This effect is particularly important in the separation of peptides and proteins that bear a number of ionizable functionalities. Hjerten and Ericson used monolithic columns with two different levels of sulfonic acid functionalities to control the proportion of EOF and electromigration. Under each specific set of conditions, the injection and detection points had to be adjusted to achieve and monitor the separation [117]. Another option consists of total suppression of the ionization. For example, an excellent separation of acidic drugs has been achieved in the ion-suppressed mode at a pH value of 1.5 [150]. 

The molecular absorption intensity of polar compounds is usually small, but highly sensitive detection can be obtained after pre- or post-column derivatiza-tions. The use of ultraviolet absorption or fluorescence-active counter-ions makes it possible to achieve highly sensitive detection of polar compounds and enhance the capability of ion-pair liquid chromatography. For example, N,N-dimethylprotriptyline has been used as a counter-ion for carboxylic acids12 and picric acid for quaternary amines13 in normal-phase ion-pair partition liquid chromatography. Phenethylammonium, cetylpyridinium, l-phenethyl-2-pyco-linium, and naphthalene-2-sulfonic acid have been used for sulfonic acid and alkyl amines detection.14,15 Ion-pair post-column extraction was applied on-line for fluorescence detection.16... 

One example is the separation of tricarboxylic acid cycle organic acids. These organic acids were originally separated on sulfonic acid-treated silica gel as the stationary phase material, and a chloroform and isopentyl alcohol mixture was used as the eluent. However, this eluent is not suitable for UV detection. A mixture of -hexane, THF, and ter/-butanol was therefore selected for the same separation.74... 

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