FADAs

FADAs are important ingredients in formulated detergents and cosmetics, since they enhance the emulsifying properties of anionic and... 

FADAs are nitrogen derivatives of coconut oil synthesised from fatty acid and diethanolamine. Equimolar amounts of the two starting compounds yield water-insoluble monoethanolamides, whereas the reaction of two moles of diethanolamine with one of the acids results in water-soluble FADA possessing the typical alkyl chain distribution with the C12/C14 homologues prevailing [33]. 

Therefore, a C13-AE, a cationic (quaternary ammonium) surfactant (quat), an amphoteric Ci2-alkylamido betaine, and the non-ionic fatty acid diethanol amide (FADA) as presented with their FIA-MS spectra in Fig. 2.5.12(a)-(d) were analysed as pure blends and as mixtures always obtained from two blends in FIA-MS multiple ion detection mode (MID). Mixtures as well as pure blends contained identical concentrations of surfactant homologues. For AE quantitation the mass traces of all A m/z 44 equally spaced homologues (m/z 306-966) of the C13-AE were recorded. The cationic (quaternary ammonium) surfactant, the amphoteric Ci2-alkylamido betaine, and the non-ionic FADA were quantified recording the mass traces at m/z 214 and 228, or 184, 212, 240, 268, 285, 296, 313, 324 and 341, or 232,260, 288, 316 and 344, respectively. 

To recognise ion suppression reactions, the AE blend was mixed together either (Fig. 2.5.13(a) and (b)) with the cationic quaternary ammonium surfactant, (c, d) the alkylamido betaine compound, or (e, f) the non-ionic FADA, respectively. Then the homologues of the pure blends and the constituents of the mixtures were quantified as presented in Fig. 2.5.13. Ionisation of their methanolic solutions was performed by APCI(+) in FIA-MS mode. The concentrations of the surfactants in the mixtures were identical with the surfactant concentrations of the blends in the methanolic solutions. Repeated injections of the pure AE blend (A 0-4.0 min), the selected compounds in the form of pure blends (B 4.0—8.8 min) and their mixtures (C 8.8— 14.0 min) were ionised and compounds were recorded in MID mode. For recognition and documentation of interferences, the results obtained were plotted as selected mass traces of AE blend (A b, d, f) and as selected mass traces of surfactant blends (B a, c, e). The comparison of signal heights (B vs. C and A vs. C) provides the information if a suppression or promotion has taken place and the areas under the signals allow semi-quantitative estimations of these effects. In this way the ionisation efficiencies for the pure blends and for the mixture of blends that had been determined by selected ion mass trace analysis as reproduced in Fig. 2.5.13, could be compared and estimated quite easily. 

If N-containing surfactants, e.g. quats, alkylamido betaine or FADA, were ionised together with AE a depression was expected for AE compounds because of the proton affinity of the amino nitrogen... 

Fig. 2.5.12. APCI-FIA-MS(+) overview spectra of industrial surfactant blends used as pure blends or mixtures in the examination of ionisation interferences, (a) C13-AE, (b) cationic (alkyl benzyl dimethyl ammonium quat) surfactant, (c) amphoteric C12-alkylamido betaine, and (d) non-ionic FADA all recorded from methanolic solutions. 

Fig. 2.5.13. Ion current traces of APCI-FIA-MS(+) examinations of compound interferences performed in multiple ion detection mode applied for quantification of pure AE blend (A AE b,d,f recorded between 0 and 4.0 min), pure quat (B a), betaine (B c) and FADA (B e) blend (cf. B Selected compounds a,c,d recorded between 4.0 and 8.5 min). In mixtures of AE with quat, betaine or FADA, respectively, all constituents were determined by MID (cf. C Mixture AE/quat (a,b), AE/betaine (c,d), and AE/FADA (e,f) (recorded between 8.5 and 14.0 min, respectively). Ions recorded in MID mode for quantification AE (all ions starting at m/z 306 + A 44 and ending at 966), quat m/z 214 and 220, betaine m/z 184, 212, 240, 268, 285, 296, 313, 324 and 341, FADA m/z 232, 260,...

An improved specificity was observed when FIA-MS-MS in product or parent ion mode was used to perform quantification of the surfactants in the methanolic mixtures. The ions selected for quantitation in product or parent ion mode were C13-AE m/z 71, 85, 99, 113, and 127 from alkyl chain together with 89, 133, and 177 from PEG chain generated from parent ions m/z 394, 526, 658, 790 and 922 alkylbenzyl dimethyl ammonium quat m/z 91 and 58 generated from parent ion m/z 214 FADA m/z 88, 106 and 227 generated from parent ions m/z 232, 260, 288, 316, 344 and 372 while the alkylamido betaine was quantified generating the parent ion m/z 343 obtained from product ion at m/z 240. 

For comparison of time necessary to quantify the compounds examined by FIA—MS and MS—MS, LC was also examined. API— LC—MS studies with RP-Cis (AE, betaine, FADA) or PLRP (quat) column applied for separation were performed. Quantitative results could be obtained with SDs < 5%, while the invested time in parallel increased by a factor > 12 compared with FIA-MS. 

Fatty acid and unsaturated fatty acid mono- and diethanolamides Fatty acid mono- (FAMA) and diethanol amides (FADA) with the general formula (C,32n+1-C(0)N(HyCH2-CH2-0H)2 x = l or 0) are presented with their general structural formulae in Fig. 2.9.28(a) and (b). These surfactants have found a widespread application in household and personal care formulations because of their quite good... 

Fig. 2.9.28. General structural formulae of saturated and unsaturated FAMA or FADA...

Fig. 2.9.32. ESI-FIA-MS-MS(+) (CID) product ion mass spectrum of parent ion with mjz 288 FADA ion C H2 +i-C(0)-N(CH2-CH2-OH)m n = 11, m = 2 (inset) fragmentation scheme observed under CID conditions [16].

A commercial blend of this FADA derivative was examined by MS-MS. The application ofESI-FIA-MS(+)tothis very pure blend resulted in a single [M + H]+ ion at m/z 370. Then ESI-FIA-MS-MS(+) was performed and the diethanolamide derivative of this unsaturated fatty acid showed a comparable behaviour to that observed with saturated diethanolamides [16], i.e. fragments with m/z 88, 106, 352 and (370-61 = 309) as shown in the CID spectrum in Fig. 2.9.33 were generated, which can then be explained as presented in the inset [24]. 

Fatty acid diethanolamides (FADAs) are used in certain household textile washing and hand dish-washing formulations. The presence of coconut diethanolamides (CDEAs) with an alkyl chain between 7 and 15 C units has been reported in municipal wastewaters in Germany at levels of 111—124 i,g L 1 [31] in influent and 14 i,gL 1 in effluent indicating approximately 90% elimination, while the monitoring of CDEAs in a Swedish WWTP indicated significantly lower removal (about 40%). Other studies [8,29,32,33] reported levels up to 470 xg L-1 in raw influents (Table 6.1.7). Very low concentrations found in effluents indicate efficient elimination (>96%), whereas nothing is known about the formation of persistent metabolites. 

DEQ DM DTD MAC EO FADA LAB LAS M MBAS MCPEG Lever s diester quat dialkyldimethyl ammonium ditallow dimethylammonium chloride ethylene oxide fatty acid diethanolamide linear alkylbenzene linear alkylbenzene sulfonate R3S1O0.5 methylene blue active substances mono carboxylated PEG... 

Hicks, J.K. et al., Aspergillus spomlation and mycotoxin production both require inactivation of the FadA G protein-dependent signaling pathway, EM BO J., 16, 4916, 1997. 

FADA — Fabrica Argentina de Armas FADEX-Fabrica Argentina de Explosivos FAPESA — Fabrica Argentina de Productos Ele ctricos Sociedad Anonima FAPOL — Fabrica Argentina de Polvoras FOTI — trade name for Manufacture Argentina de Polvoras ... 

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