Amino acid surfactants cationic

Reductions can also be performed in water. Systems for reduction of ketones in water can be water-compatible sodium and lithium borohydrides, amino acid-based cationic surfactants to reduce aryl ketones [19], iridium hydrides used in transfer hydrogenations, such as [Cp Irm(bpy)H]+ (Cp — q5-C5Mes, bpy = 2,2 - bipyridine) [20], and IrHCI2(cod) 2 with a chiral diaminodiphosphine ligand to form secondary alcohols in high enantioselectivity and almost quantitative yield (Equation 4.12) [21]. 

The term amphoteric (from amphos, meaning both) was first used for surfactants in the 1940s by H. Mannheimer (5). Amphoterics are substances which can have - like an amino acid - anionic, cationic or zwitterionic properties. These three forms exist in an equilibrium, depending on the pH range (Figure 15.1). At an acidic pH, the molecules will be protonated to form cations, while at an alkaline pH they will be depro-tonated to form anionic species. Only in a mid-pH range can they exist as neutral molecules and demonstrate their zwitterionic character. This pH is called the isoelectric point. Amphoteric behaviour requires the presence of a secondary or tertiary amine group, which can be protonated easily. 

Hidaka et al. [77] reported that amphoteric Af-(2-hydroxyethyl)- -(2-hydroxyalkyl)-P-alanines s cmc values greatly depend on the nature of the electrolytes added to its nearly neutral aqueous solution, and that the cmc value decreased in the following order NaCl > CaClj > Na2S04. Also, their calcium stability is superior to that of A-dodecyl-P-alanines. The effect of pH on this amphoteric amino acid surfactant was smdied in the presence of 0.1 M NaCl [78] and the results showed that the cmc value increased on the acidic side below the isoelectric point pi = 6.8 and remained almost unchanged on the alkaline side. Examination of the configuration with molecular models indicates that the cationic ionization of the amino group on the acidic side probably takes place within the micelle, whereas under alkaline circumstances the anionic ionization of the carbonyl group occurs on the micellar surface. This makes the electrostatic potential for ionization different on the acidic and alkaline sides. 

TABLE 3 Amino Acid-Based Cationic Surfactants on the Market... 

Isocyanide polymers functionalized with amino acid groups, typically di-or tripeptides containing histidine or serine, give enantioselective deacylation and rate enhancements. Their activity is increased by addition of cationic surfactants (Visser et al., 1985). 

Anions and uncharged analytes tend to spend more time in the buffered solution and as a result their movement relates to this. While these are useful generalizations, various factors contribute to the migration order of the analytes. These include the anionic or cationic nature of the surfactant, the influence of electroendosmosis, the properties of the buffer, the contributions of electrostatic versus hydrophobic interactions and the electrophoretic mobility of the native analyte. In addition, organic modifiers, e.g. methanol, acetonitrile and tetrahydrofuran are used to enhance separations and these increase the affinity of the more hydrophobic analytes for the liquid rather than the micellar phase. The effect of chirality of the analyte on its interaction with the micelles is utilized to separate enantiomers that either are already present in a sample or have been chemically produced. Such pre-capillary derivatization has been used to produce chiral amino acids for capillary electrophoresis. An alternative approach to chiral separations is the incorporation of additives such as cyclodextrins in the buffer solution. 

Small ACTH fragments related to ACTH-(4-10) have also been investigated for the presence of ordered structure. CD of ACTH--(5-10) in TFE showed a random structure (50) as was found with H-NMR for fragment 4-10 (51). The addition of anionic or cationic surfactants to an aqueous solution of ACTH-(4-11) dit not promote any a-helix or 3-form in this peptide (CD experiments S2). When ACTH-(1-14) and 1-10 were measured by CD and NMR respectively, indications for a helical or ordered structure were found (90, ). Thus it seems that the addition of the non-helix "prone" fragment 1-3 or 1-4 can promote the formation of a helical structure in the adjacent sequence. Arguments in favour of this come from the theoretical work of Argos and Palau (53) on amino acid distribution in protein secondary structures. They found that Ser and Thr frequently occur at the N-terminal helical position (cf. Ser in ACTH) to provide stability the position adjacent to the helical C-terminus is often occupied by Gly or Pro (adjacent toTrp in ACTH we have Gly ) acidic amino acid residues are frequently found at the helix N-terminus (cf. Glu in ACTH) and/or basic residues at the C-terminus (cf. Arg ). 

A few years ago, we began a research program to develop methods of analysis which would involve the use of FAB and a high performance tandem mass spectrometer. The tandem instrument was the first triple sector mass spectrometer to be designed and built by a commercial instrument company (Kratos of Manchester, U.K.). The first mass spectrometer of the combination is a double focussing Kratos MS-50 which is coupled to a low resolution electrostatic analyzer, which serves as the second mass spectrometer U). This FAB MS-MS combination has been used to verify the structures of an unknown cyclic peptide (2), a new amino acid modified by diphtheria toxin (3), and an ornithine-containing lipid (4). A number of methods have also been worked out which rely on this instrumentation. They Include the structural determination of cyclic peptides (5), nucleosides and nucleotides (6), and unsaturated fatty acids (7) and the analysis of mixtures of both anionic (8) and cationic surfactants (9). 

In terrestrial systems, numerous factors have been recognized as essential in determining a herbivore s gut environment, and, hence, its response to tannins. In marine systems, many of these same factors may impact the activity of phlorotannins in the herbivore gut. These include gut morphology 44 pH,25 redox potential,58 124 166 enzyme composition and activity,33 57 surfactant type and concentration,70 160 167 cation type and concentration,70 124168 proteins or amino acids,169-175 gut microbial activity,49 50 67 and nutritional status.33... 

Most systems examined to date have employed the AOT anionic reversed micellar system (366-370). In one case, amylase was extracted using trioctylmethylammonium chloride (cationic surfactant) in isooctane (375) while in another, catalase was extracted using a cationic DTAB/octane/hexanol reversed micelle (377). In our own research, we have successfully employed nonionic Igepal CO-530 -CCl, cationic CTAB - hexanol, and zwitterionic lecithin - CC1, reversed micellar systems in the extraction of some amino acids and proteins (379). The availability of such a pool of different charge-type micellar systems allows one flexibility in the development of such extraction schemes. In fact, preliminary results seem to indicate that better extractions are obtainable in some instances via use of zwitterionic reversed micellar media (379). 

H -tetramethylbenzidine in anionic-cationic mixed micelles has been studied in detail by ESR . The photochemistry of the semi-oxidised forms of eosin Y and rose bengal have been investigated in colloidal solutions. Relevant to the fluorescence of proteins is a study of fluorescence quenching of indolic compounds by amino-acids in SOS, CTAB, and CTAC micelles O Rate constants for proton transfer of several hydroxyaromatic compounds have been measured in a variety of surfactant solutions. Photoprotolytic dissociation does not require exit of the reactant molecules from the micelles. Micellar solutions can be used to improve the fluorescence determination of 2-naphthol by inhibiting proton transfer or proton inducing reactions z2. jpe decay of the radical pair composed of diphenylphosphonyl and 2,4,6-trimethyl benzoyl radicals in SDS is affected by magnetic... 

Probes currently employed in the indirect UV detection of amino acids include p-aminosalicylic acid, benzoic acid, phthalic acid, sodium chromate, 4-(N,N -dimethylamino)benzoic acid, 1,2,4,-benzenetricar-boxylic acid (trimellitic acid), 1,2,4,5-benzenetetracar-boxylic acid (pyromellitic acid), and quinine sulfate. Several of these probes are employed in combination with metal cations and cationic surfactants, which are incorporated into the electrolyte solution as modifiers of the electro-osmotic flow. 

The reversal of the direction of the electro-osmotic flow by the adsorption onto the capillary wall of alky-lammonium surfactants and polymeric ion-pair agents incorporated into the electrolyte solution is widely employed in capillary zone electrophoresis (CZE) of organic acids, amino acids, and metal ions. The dependence of the electro-osmotic mobility on the concentration of these additives has been interpreted on the basis of the model proposed by Fuerstenau [6] to explain the adsorption of alkylammonium salts on quartz. According to this model, the adsorption in the Stern layer as individual ions of surfactant molecules in dilute solution results from the electrostatic attraction between the head groups of the surfactant and the ionized silanol groups at the surface of the capillary wall. As the concentration of the surfactant in the solution is increased, the concentration of the adsorbed alkylammonium ions increases too and reaches a critical concentration at which the van der Waals attraction forces between the hydrocarbon chains of adsorbed and free-surfactant molecules in solution cause their association into hemimicelles (i.e., pairs of surfactant molecules with one cationic group directed toward the capillary wall and the other directed out into the solution). 

Jursic, B. S., Neumann, D. Preparation of N-acyl derivatives of amino acids from acyl chlorides and amino acids in the presence of cationic surfactants. A variation of the Schotten-Baumann method of benzoylation of amino acids. Synth. Common. 2001, 31, 555-564. 

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