Cetyltrimethylammonium cations

This paper addresses two issues concerning practical aspects of synthesis and utility of pillared zeolites. First it shows how to demonstrate that the observed mesoporous attributes of a particular preparation are not due to undesired M41S contamination. This possibility arises because of the similarity of synthesis regime in both cases aluminosilicate substrates treated with cationic surfactant at high pH and temperature. Second issue concerns the benefits of pillaring zeolite precursor as manifested via improved catalytic performance. Herein we compare the properties of MCM-41 and the pillared zeolite MCM-36 obtained with cetyltrimethylammonium cation as the swelling/templating surfactant. 

Both types of molecular sieves, MCM-36 and MCM-41, demonstrate large BET surface area and high static sorption capacity (see Table 2). Considerable qualitative differences are observed in N2 isotherms, which are shown in Figure 3. The nitrogen isotherm for MCM-41, prepared with cetyltrimethylammonium cation, is type IV [9] and shows the characteristic reversible steep capillary condensation at p/p0 = -0.4 corresponding to the pore opening -40 A [1]. MCM-36 also shows the type IV isotherm with almost linear and reversible uptake increase up to - p/p0 = 0.5, followed by a hysteresis loop. This profile of adsorption/desorption is typical for layered materials with slit-like porosity generated between layers [9],... 

Ionic compounds can also gelate solvents, perhaps one of the nicest examples being that of dicationic gemini surfactants in which tartrate is used as the counterion and source of chirality [158], because it shows the very important role of chirality on the property of the salt. When either d- or L-tartrate dianions and dimers of cetyltrimethylammonium cations are combined, stable gels are formed in chlorinated solvents, but neither the mixture of enantiomers nor the meso tartrate form a gel. The structure of the gelator... 

Wang, W. et al., Adsorption and structural arrangement of cetyltrimethylammonium cations at the sihca nanoparticle-water interface, J. Phys. Chem. B.. 108, 17477, 2004. 

In this section the influence of micelles of cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and dodecyl heptaoxyethylene ether (C12E7) on the Diels-Alder reaction of 5.1a-g with 5.2 in the absence of Lewis-add catalysts is described (see Scheme 5.1). Note that the dienophiles can be divided into nonionic (5.1a-e), anionic (5.If) and cationic (5.1g) species. A comparison of the effect of nonionic (C12E7), anionic (SDS) and cationic (CTAB) micelles on the rates of their reaction with 5.2 will assess of the importance of electrostatic interactions in micellar catalysis or inhibition. 

Peculiar DNA architecture was demonstrated in 25% aqueous ethanol when DNA was complexed with series of cationic detergents in the presence of poly(glutamic acid) [124]. Electron microscopy and x-ray scattering demonstrated that DNA can pack cetyltrimethylammonium bromide molecules into rodlike micelles, which form a hexagonal lattice. Interestingly, circular dichroism spectroscopy revealed that in these complexes DNA adopts left-handed conformation. 

Kuczynski and Thorns also studied the formation of MV in CdS solution using a cationic surfactant, cetyltrimethylammonium bromide, as a stabiliasr. In the presence of ethylenediaminetetraacetate (EOTA), the MV " yield was greatly increased. EDTA and MV " form a complex with a resultant negative charge, which is electrostatically bound to the cationic CdS surface. The MV " formed is repelled by the positive charge of the cationic stabilizer, a fact which makes the charge separation efficient. 

Photoinduced ET at liquid-liquid interfaces has been widely recognized as a model system for natural photosynthesis and heterogeneous photocatalysis [114-119]. One of the key aspects of photochemical reactions in these systems is that the efficiency of product separation can be enhanced by differences in solvation energy, diminishing the probability of a back electron-transfer process (see Fig. 11). For instance, Brugger and Gratzel reported that the efficiency of the photoreduction of the amphiphilic methyl viologen by Ru(bpy)3+ is effectively enhanced in the presence of cationic micelles formed by cetyltrimethylammonium chloride [120]. Flash photolysis studies indicated that while the kinetics of the photoinduced reaction,... 

The Henry (nitroaldol) reaction was reported under very mild reaction conditions, in aqueous media using a stoichiometric amount of a nitroalkane and an aldehyde, in NaOH 0.025 M and in the presence of cetyltrimethylammonium chloride (CTAC1) as cationic surfactant (Eq. 8.94) 240 Good to excellent yields of (i-nitroalkanol are obtained. Under these conditions several functionalities are preserved, and side-reactions such as retro-aldol reaction or dehydration of 2-nitroalcohols are avoided. 

The nitro-aldol reaction can also be carried out in water using NaOH in the presence of cetyltrimethylammonium chloride (CTAC1) as a cationic surfactant. CTAC1 (5 mmol) is added to a mixture of nitroalkane (50 mmol) and aldehyde (50 mmol) in NaOH 0.025 M (150 mL) at room temperature. The mixture is stirred for 2-3 h and worked up to give the product in 70-90% yield. Compared with the classical methods, this procedure has economical and environmental advantages (Eq. 3.16).27... 

In recent years, there has been increased recognition that water is an attractive medium for organic reactions from the environmental point of view. The Michael addition of various nitroalkanes to conjugated enones can be performed in NaOH (0.025 M) and in the presence of cetyltrimethylammonium chloride (CTAC1) as cationic surfactant in the absence of organic solvents (Eq. 4.109).146 The Michael addition of nitromethane to methyl acrylate is carried out in water using NaOH as a base to give the mono adduct (Table 4.2).147... 

Recently, a detailed study was reported for a molecularly ordered layered silicate surfactant mesophase [125, 126]. A subtle change in the surfactant which is used for the synthesis of such mesophases appears to induce dramatic modifications in the silica ordering. When cetyltrimethylammonium (C16NMe3+) cations are employed, then only two 29Si NMR resonances at —102 ppm (Q3) and... 

Howard [27] determined dissolved aluminium in seawater by the micelle-enhanced fluorescence of its lumogallion complex. Several surfactants (to enhance fluorescence and minimise interferences), used for the determination of aluminium at very low concentrations (below 0.5 pg/1) in seawaters, were compared. The surfactants tested in preliminary studies were anionic (sodium lauryl sulfate), non-ionic (Triton X-100, Nonidet P42, NOPCO, and Tergital XD), and cationic (cetyltrimethylammonium bromide). Based on the degree of fluorescence enhancement and ease of use, Triton X-100 was selected for further study. Sample solutions (25 ml) in polyethylene bottles were mixed with acetate buffer (pH 4.7, 2 ml) lumogallion solution (0.02%, 0.3 ml) and 1,10-phenanthroline (1.0 ml to mask interferences from iron). Samples were heated to 80 °C for 1.5 h, cooled, and shaken with neat surfactant (0.15 ml) before fluorescence measurements were made. This procedure had a detection limit at the 0.02 pg/1 level. The method was independent of salinity and could therefore be used for both freshwater and seawater samples. 

Equation (1) is generally used to estimate the rate constant, kin the micellar pseudophase, but for inhibited bimolecular reactions it provides an indirect method for estimation of otherwise inaccessible rate constants in water. Oxidation of a ferrocene to the corresponding ferricinium ion by Fe3 + is speeded by anionic micelles of SDS and inhibited by cationic micelles of cetyltrimethylammonium bromide or nitrate (Bunton and Cerichelli, 1980). The variation of the rate constants with [surfactant] fits the quantitative treatment described on p. 225. Oxidation of ferrocene by ferricyanide ion in water is too fast to be easily followed kinetically, but the reaction is strongly inhibited by anionic micelles of SDS which bind ferrocene, but exclude ferricyanide ion. Thus reaction occurs essentially quantitatively in the aqueous pseudophase, and the overall rate depends upon the rate constant in water and the distribution of ferrocene between water and the micelles. It is easy therefore to calculate the rate constant in water from this micellar inhibition. 

Spontaneous hydrolyses of carboxylic anhydrides, diaryl carbonates and aryl chloroformates are faster in cationic than in anionic micelles, regardless of the nature of the counteranion in the cetyltrimethylammonium micelle (Al-Lohedan et al., 1982b Bunton et al., 1984). This charge effect does not seem to be related to substrate hydrophobicity, although the extent of micellar inhibition (relative to reaction in water) is clearly dependent upon substrate hydrophobicity for anhydride hydrolyses. 

Because of the differential partitioning of hydroxide and phenoxide anions into organic solvents by quaternary ammonium cations, the catalysts generally have little effect on the Reimer-Tiemann reaction of phenols with dihalocarbenes [15]. Cetyltrimethylammonium bromide has been used in the two-phase dichloromethyl-ation of polysubstituted phenols (Scheme 7.21, Table 7.10) under Makosza s conditions [16,17] ring expansion of the reaction products provides an effective route to tropones. The rate of the reaction is enhanced by ultrasonic radiation [16]. 

A wide choice of cationic surfactants such as CTAB (cetyltrimethylammonium bromide), CTAH (cetyltrimethylammonium hydroxide), TTAB (tetradecyltrimethylammonium bromide), TTAOH (tetradecyltrimethylammonium hydroxide), MTAB (myristyltrimethylammo-nium bromide), OFM (OFM Anion-BT, Waters, Milford, MA, USA), HDB (hexadimethrine bromide), and many others may be used to reverse the EOF. CTAH and TTAOH should be preferred to CTAB and TTAB to avoid interference from bromate contamination. The capillary coating is performed just by rinsing with the BGE containing this flow modifier or even with an additional rinse step with a solution containing this flow modifier. 

The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyl-trimethylammonium bromide (TTABr) and sodium dodecyl sulfate (SDS) on the rates of alkaline hydrolysis of securinine (223) were studied at a constant [HO ] (0.05 m). An increase in the total concentrations of CTABr, TTABr and SDS from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, and 7, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelles. Cationic micelles of CTABr speed attack of hydroxide ion upon coumarin (224) twofold owing to a concentration effect. ... 

Liu and Rauch (2003) of Motorola investigated oligonucleotide probe attachment onto polystyrene (PS), polycarbonate (PC), polymethyl methacrylate (PMMA), and polypropylene (PP) plastic surfaces. They utilized three different immobilization processes SurModics surface modification solution (that allows attachment of adsorbed reactive groups to a surface by photoactivation of polymers at 254 nm). Pierce Reactive-Bind coating solution, and CTAB (cetyltrimethylammonium bromide, a cationic detergent). Not surprisingly, the microarray performances on these plastics varied. 

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