Methanol-water complex

Zhao, Z. and Malinowski, E.R., Detection and identification of a methanol-water complex by factor analysis of infrared spectra, Anal. Chem., 71, 602-608, 1999. 

This overview analyzes the electron redistribution that takes place in two interacting monomers upon H-bond formation. The systems selected (shown in Fig. 1) focus on the two most important classical H-bonds, O-H- O and N H- O, and cover both donor and acceptor roles of every monomer. They are the following (a) water dimer (WD), (b) methanol water complex (MW), (c) water methanol complex (WM), (d) formic acid dimer (FAD), (e) forma-mide dimer (FD), and (f) formamide-formic acid complex (FFAC). Systems (a)-(c) are bound by one single O-H- 0 bond whereas cyclic dimers (d)-(l) are linked by two H-bonds. In FAD and FD homodimers, both monomers behave simultaneously as donor and acceptor while in the FFAC heterodimer, for-mamide and formic acid play competing roles. 

Table 9.3 Vibrational frequencies and IR intensities for methanol-water complex...

Silica gel, per se, is not so frequently used in LC as the reversed phases or the bonded phases, because silica separates substances largely by polar interactions with the silanol groups on the silica surface. In contrast, the reversed and bonded phases separate material largely by interactions with the dispersive components of the solute. As the dispersive character of substances, in general, vary more subtly than does their polar character, the reversed and bonded phases are usually preferred. In addition, silica has a significant solubility in many solvents, particularly aqueous solvents and, thus, silica columns can be less stable than those packed with bonded phases. The analytical procedure can be a little more complex and costly with silica gel columns as, in general, a wider variety of more expensive solvents are required. Reversed and bonded phases utilize blended solvents such as hexane/ethanol, methanol/water or acetonitrile/water mixtures as the mobile phase and, consequently, are considerably more economical. Nevertheless, silica gel has certain areas of application for which it is particularly useful and is very effective for separating polarizable substances such as the polynuclear aromatic hydrocarbons and substances... 

The macrocyclic antibiotic-based CSPs have not been used extensively in SFC. Two macrocyclic antibiotic CSPs, Chirobiotic T and Chirobiotic V, were included in a study of various CSPs in SFC. At least partial resolution of approximately half of the 44 test compounds could be obtained on these two CSPs in SFC [63]. A high concentration of modifier was necessary to elute some of the analytes. Enantioreso-lution of derivatized amino acids was also demonstrated in the same study. Flowever, a complex modifier comprised of methanol, water, and glycerol was required for separations performed on the Chirobiotic T CSP. The separation of coumachlor enantiomers on a vancomycin-based CSP (Chirobiotic V) in SFC is illustrated in Fig. 12-5 [32]. 

The association of methanol and water was examined by Katz, Lochmiiller and Scott (11) using volume change on mixing and refractive index data and established that the methanol/water solvent system was indeed a complex ternary system. 

Addition of sodium hydroxide to a mixture of [Co"(DMG)2] and an alkylating agent in methanol-water yields up to 50% of the organocobalt product. This appears to be the most convenient method for the preparation of organocobalt(III) derivatives, provided that the maximum yield is not required 161,163). Methods involving the reaction of Co with electrophiles are, at least with DMG complexes, more convenient than the main alternative route via Co(III) and Grignard reagents. 

More recently, the same type of hgand was used to form chiral iridium complexes, which were used as catalysts in the hydrogenation of ketones. The inclusion of hydrophihc substituents in the aromatic rings of the diphenylethylenediamine (Fig. 23) allowed the use of the corresponding complexes in water or water/alcohol solutions [72]. This method was optimized in order to recover and reuse the aqueous solution of the catalyst after product extraction with pentane. The combination of chiral 1,2-bis(p-methoxyphenyl)-N,M -dimethylethylenediamine and triethyleneglycol monomethyl ether in methanol/water was shown to be the best method, with up to six runs with total acetophenone conversion and 65-68% ee. Only in the seventh run did the yield and the enantioselectivity decrease slightly. 

FIGURE 12.4 (A) Diagrammatic representation of the separation of major simple lipid classes on silica gel TLC — solvent system hexane diethylether formic acid (80 20 2) (CE = cholesteryl esters, WE = wax esters, HC = hydrocarbon, EEA = free fatty acids, TG = triacylglycerol, CHO = cholesterol, DG = diacylglycerol, PL = phospholipids and other complex lipids). (B) Diagrammatic representation of the separation of major phospholipids on silica gel TLC — solvent sytem chloroform methanol water (70 30 3) (PA = phosphatidic acid, PE = phosphatidylethanolamine, PS = phosphatidylserine, PC = phosphatidylcholine, SPM = sphingomyelin, LPC = Lysophosphatidylcholine). 

Crystal structures of dinickel complexes with 0,0-bridging and 0,N-bridging (O-methylated) carbamate have been reported.2074,20 (874) produces one equivalent of ammonia upon heating in methanol/water solution.2082... 

Mapsi et al. [16] reported the use of a potentiometric method for the determination of the stability constants of miconazole complexes with iron(II), iron(III), cobalt(II), nickel(II), copper(II), and zinc(II) ions. The interaction of miconazole with the ions was determined potentiometrically in methanol-water (90 10) at an ionic force of 0.16 and at 20 °C. The coordination number of iron, cobalt, and nickel was 6 copper and zinc show a coordination number of 4. The values of the respected log jSn of these complexes were calculated by an improved Scatchard (1949) method and they are in agreement with the Irving-Williams (1953) series of Fe2+ < Co2+ < Ni2 < Cu2+ < Zn2+. 

Figure 6.3. Stability constants for the 1 1 potassium complexes of some polyether ligands at 25 °C. The values for (223) and (169) were determined in methanol those for 2.2.2, (276) and (277) in methanol/water (95 5).

Stability constants for a series of M2+ cations, including Ca2+, with A23187 and with ionomycin have been determined in methanol-water mixtures (Taylor, R. W. Pfeiffer, D. R. Chapman, C. J. Craig, M. E. Thomas, T. P. Pure Appl. Chem. 1993, 65, 579-584) the estimation of stability constants for complexes of the anti-fungal antibiotic pradimicin (BMY-28864) with alkaline earth cations is complicated by the tendency of this antibiotic to aggregate (Hu, M. Ishizuka, Y. Igarashi, Y. Oki, T. Nakanishi, H. Spectrochim. Acta A 1999, 56, 181-191). 

In spite of the significant differences in the catalysts and conditions applied, essentially the same kinetic model was proposed for the catalytic reactions with two pyrazolate-bridged dicopper(II) complexes, [Cu2(LEP)2]2+ and [Cu2(BLEP)(OH)]2+ in 1 1 methanol-water mixture (47). The product was confirmed to be 3,5-di-ter -butyl-l,2-benzoquinone (DTBQ). 

N. Seurre, J. Sepiof, F. Lahmani, A. Zehnacker Rentien, and K. Le Barbu Debus, Vibrational study of the So and Si states of 2 naphthyl 1 ethanol/ (water)2 and 2 naphthyl 1 ethanol/ (methanol)2 complexes by IR/UV double resonance spectroscopy. Phys. Chem. Chem. Phys. 6, 4658 4664 (2004). 

The study of Lehn s cryptands has shown that a three-dimensional arrangement of binding sites leads to very stable inclusion complexes (cryptates) with many cations. For example, the stability constant for K+ in methanol/water (95/5) is five orders of magnitude higher with [2.2.2]-cryptand [37] (log K 9.75 Lehn and Sauvage, 1975) than with [2.2]-cryptand [38] (log... 

Diaza-18-crown-6 substituted with 5-chloro-8-hydroxyquinoline exhibits very interesting complexing properties. For instance, M-6 is very selective for Ba2+ over other alkaline earth cations and for K+ over Na+ in methanol. Unfortunately, investigation of fluorogenic effects with other cations has not been reported. On the other hand, the fluorescence intensity of M-7 was shown to increase by a factor of 1000 in the presence of Mg2+ (in a mixture of methanol/water 1 1 v/v) whereas other alkaline earth ions have no effect. 

Fig. 9. Normalized solubilities of l,2-dimethyl-3-hydroxy-4-pyridinone, dmppH, of its aluminum(III) and iron(III) complexes AKdmppla and Fe(dmpp)s, and of the 3-hydroxy-4-pyronate complexes Ga(malt)3 and In(etmalt)3 in methanol-water mixtures at 298.2 K (data from Refs. (114) and (234)).

The presence of a covalent acyl-enzyme intermediate in the catalytic reaction of the serine proteases made this class of enzymes an attractive candidate for the initial attempt at using subzero temperatures to study an enzymatic mechanism. Elastase was chosen because it is easy to crystallize, diffracts to high resolution, has an active site which is accessible to small molecules diffusing through the crystal lattice, and is stable in high concentrations of cryoprotective solvents. The strategy used in the elastase experiment was to first determine in solution the exact conditions of temperature, organic solvent, and proton activity needed to stabilize an acyl-enzyme intermediate for sufficient time for X-ray data collection, and then to prepare the complex in the preformed, cooled crystal. Solution studies were carried out in the laboratory of Professor A. L. Fink, and were summarized in Section II,A,3. Briefly, it was shown that the chromophoric substrate -carbobenzoxy-L-alanyl-/>-nitrophenyl ester would react with elastase in both solution and in crystals in 70 30 methanol-water at pH 5.2 to form a productive covalent complex. These... 

Structures have been determined for [Fe(gmi)3](BF4)2 (gmi = MeN=CHCF[=NMe), the iron(II) tris-diazabutadiene-cage complex of (79) generated from cyclohexanedione rather than from biacetyl, and [Fe(apmi)3][Fe(CN)5(N0)] 4F[20, where apmi is the Schiff base from 2-acetylpyridine and methylamine. Rate constants for mer fac isomerization of [Fe(apmi)3] " were estimated indirectly from base hydrolysis kinetics, studied for this and other Schiff base complexes in methanol-water mixtures. The attenuation by the —CH2— spacer of substituent effects on rate constants for base hydrolysis of complexes [Fe(sb)3] has been assessed for pairs of Schiff base complexes derived from substituted benzylamines and their aniline analogues. It is generally believed that iron(II) Schiff base complexes are formed by a template mechanism on the Fe " ", but isolation of a precursor in which two molecules of Schiff base and one molecule of 2-acetylpyridine are coordinated to Fe + suggests that Schiff base formation in the presence of this ion probably occurs by attack of the amine at coordinated, and thereby activated, ketone rather than by a true template reaction. ... 

Transfer chemical potentials for the low-spin amine-diimine complexes [Fe(tsba)2] " with tsba = (8 were estimated from the solubilities of their perchlorate salts, in methanol-water mixtures.Solubility and transfer chemical potential data are also available for [Fe(Me2bsb)3] " " in several nonaqueous solvents. One of the main purposes in determining transfer chemical potentials for these iron(II)-diimine complexes is to enable dissection of reactivity trends into initial state and transition state components for base hydrolysis (see next section) in binary aqueous solvent mixtures. Systems for which this has been achieved are indicated in Table 8. 

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