Pinacyanol chloride

In a study looking at solvent stability [424], various aqueous-miscible solvents (tetrahydrofuran, acetonitrile, isopropanol, methanol, and A,A-dimethylformamide) were used with pinacyanol chloride as substrate. Although a PAH was not used as a substrate, the results may be extrapolated to PAH reactions. The greater impact of peroxide as compared to the solvent on biocatalyst stability was reported in this study and the need to control peroxide concentration was noted. 

Batchelor EK, Gadde S, Kaifer AE (2010) Host-guest control on the formation of pinacyanol chloride H-aggregates in anionic polyelectrolyte solutions. Supramol Chem 22 40-45... 

To estimate how many dye molecules fit into the dendritic micelles, UV-titra-tion experiments have been employed. In comparison with the spectra of a pure pinacyanol chloride solution in water, the peaks of the absorption maxima of the dye in the presence of the dendrimer are shifted bathochromically due to solvatochromic effects, which indicates the incorporation of the dye within the branches of the dendrimer. At dye-to-dendrimer molar ratios higher than 4 1, in addition to the bathochromic shifts, hypsochromically shifted peaks start to appear, indicating that the dendrimer is not incorporating further dyes. We interpret this as an incorporation of up to four dyes within the branches of the dendrimer. This observation correlates with the calculated available space within the dendrimer, obtained from the molecular simulations. Further studies of the interactions of the dyes within the dendritic micelle are in progress. 

Figure9.8 The absorbance of 1.05 x 10 M pinacyanol chloride at 610.0 min pH 9.59 sodium borate buffer (I = 0.1) at 50 °C vs. dodecanoate concentration. The absorption spectrum of pinacyanol chloride in aqueous solution of anionic soaps changes sharply to one characteristic of its solutions in organic solvents within a small range of soap concentration (X ax 610 nm). This effect is attributed to the formation of micelles, in whose hydrocarbon-like layers or cores the dye is solubilized. The concentration of soap at which this spectral change occurs is taken as the cmc. The use of dyes for the determination of cmc values may lead to micelle formation at a concentration below the true cmc. In practice, the method gives only a rough approximation of the cmc. (Adapted, with some modifications, from Corrin et al., 1946.)...

Corrin, M. L Klevens, H. B and Harkins, D. (1946). The determination of critical concentrations for the formation of soap micelles by the spectral behavior of pinacyanol chloride. J. Chem. Phys., 14,480-6. 

Pinacyanol chloride [2768-90-3] M 388.9, m 270°(dec). Crystd from EtOH/ethyl ether. 

The unimolecular micellar characteristics of this poly(ammonium carboxylate) 156 were demonstrated 179 by UV analysis of guest molecules, such as pinacyanol chloride, phenol blue, and naphthalene combined with fluorescence lifetime decay experiments employing diphenylhexatriene as a molecular probe. The monodispersity, or absence of intermolecular aggregation, and molecular size were determined by electron microscopy. 

Molecular inclusion was demonstrated by the aqueous solubilization and UV and fluorescence analysis of the guest dyes phenol blue (8), pinacyanol chloride (9). chlortetracycline (10).and naphthalene (11).Fluorescence lifetime decay experiments using 1,6-diphenylhexatriene (12) as the probe further supported the host-guest relationship while electron microscopy (EM) coirobo-rated the single molecule, non-aggregated state. Calculated molecular modeling diameters o/48 A in a fully extended conformation were also substantiated via EM. 

Dendrimers as Micelles, in their seminal work, Newkome and coworkers designed and synthesized a dendrimer called micellanoic acid with an allhydrocarbon interior and carboxylic acid periphery (Fig. 23) (78). They showed that these dendrimers are water-soluble and are capable of sequestering hydrophobic substituents in their interior. The guest molecules include spectral probes such as phenol blue, naphthalene, pinacyanol chloride, and diphenylhexatriene. By comparison with classical amphiphiles such as SDS, it was shown that the critical micelle concentration (cmc) of these dendrimers is very low. Therefore, they called these dendrimers as unimolecular micelles (79). Binding abilities of some of these amphiphilic dendrimers have also been investigated using electrokinetic chromatography and electrochemistry (80-83). 

The decomposition of pinacyanol chloride dye using octahedral layered mixed-valent manganese oxides has been published [81]. Catalytic reduction reactions using birnessite have been tried for removing pentachlorophenol (PCP) from soil and water (detoxyfication) [82]. Transformation and dechlorination of PCP incubated with peroxidase, laccase, or birnessite is decreased in the presence of humic monomers as cosubstrate. The dehalogenation number for birnessite is 3.3, compared with 3.5 for peroxidase and 1.5 for laccase [82]. 

Horwitz et al. developed nonheme iron complexes with tetraamido macrocyclic ligands (TAML) that are efficient for the dye bleaching reactions with HjOj in water from neutral to basic Pinacyanol chloride as a reference,... 

When micelles form in the solution Ni is partitioned out of the bulk into the vicinity of the charged micelle surface. Binding of NiMu" is unlikely since the ion is hydrophilic and singly charged [89]. The nickel murexide systems, therefore, operate somewhat differently from indicator dyes such as Acridine Orange and Pinacyanol Chloride which are lipophilic and are either solubilized by the micelle or adsorbed on to the surface. The chromophore in the murexide system remains in the bulk phase. 

Meanwhile, pinacyanol chloride, a kind of pigment, has two visible absorption maxima, the a-band (AmarOOb nm) and / -band (A iaar550 nm). These shift to longer wavelengths with increasing molar extinction... 

In 1956, Fuerstenau coined the term hemimicelle to describe the two-dimensional aggregates that he proposed were responsible for the rise through several orders of magnitude in the observed absorption of surfactant molecules on certain mineral oxide surfaces from aqueous solutions. The study on coadsorption of pinacyanol chloride (cyanine dye) with sodium p-(l-propylnonyl)-benzenesulfonate (dissolved in water) on AI2O3 surface reveals that surfactant adsorption is independent of the concentration of pinacyanol chloride, and the surfactant solution remains clear at total surfactant concentration ([SurfJx) below CMC, whereas the solid surface becomes dyed blue, the color characteristic of... 

Nunn, C.C., Schechter, R.S., Wade, W.H. Visual evidence regarding the nature of hemimiceUes through surface soluhihzation of pinacyanol chloride. J. Phys. Chem. 1982, 86(16), 3271-3272. 

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