Effects of alcohols on micellization and on the reaction methyl 4‐nitrobenzenesulfonate + Br− in cetyltrimethylammonium bromide aqueous micellar solutions

The effects of n‐hexanol, n‐pentanol, and n‐butanol on the critical micelle concentration (cmc), on the micellar ionization degree (α), and on the rate of the reaction methyl 4‐nitrobenzenesulfonate + Br^? have been investigated in cetyltrimethylammonium bromide (CTAB) aqueous solutions. An increase in the alcohol concentration present in the solution produces a decrease in the cmc and an increase in the micellar ionization degree. Kinetic data show that the observed rate constant decreases as alcohol concentration increases. This result was rationalized by considering variations in the equilibrium binding constant of the methyl 4‐nitrobenzenesulfonate molecules to the micelles, variations in the interfacial bromide ion concentration, and variations in the characteristics of the water–alcohol bulk phase provoked by the presence of alcohols. When these operative factors are considered, kinetic data in this and other works show that the second‐order rate constants in the micellar pseudophases of water–alcohol micellar solutions are quite similar to those estimated in the absence of alcohols. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 634–641, 2004     

Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.     

Columnar bis(pyridinium) ionic liquid crystals derived from 4-hydroxypyridine: synthesis,mesomorphism and emission properties

A series of flexibly linked bis(pyridinium) salts with various counterions (Br^?, PF₆^?, BF₄^? and OTf-) was designed and prepared starting from corresponding N-alkylated 4-pyridones precursors with mesogenic 3,4,5-tris(alkyloxy)benzyl moieties (alkyl = dodecyl or tetradecyl). These salts were investigated for their liquid crystalline properties by a combination of differential scanning calorimetry, polarising optical microscopy and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was checked by thermogravimetric analysis. All bis(pyridinium) salts, except the triflate salt with shorter terminal carbon chain, display an enantiotropic liquid crystalline behaviour with a hexagonal columnar (Col_h) phase assigned on the basis of its characteristic texture and XRD studies. It was found that these luminescent bis(pyridinium) salts show weak emission in dichloromethane solutions at room temperature and a pronounced red-shifted emission in solid state. The emission properties of these bis(pyridinium) salts do not depend significantly on the nature of counterion employed.     

Pomegranate By-Products as Natural Preservative to Prolong the Shelf Life of Breaded Cod Stick

This work evaluated the efficacy of pomegranate byproducts, specifically peel powder, as valid preservatives for food quality. Ready-to-cook cod sticks breaded with pomegranate peel powder were prepared. Shelf-life tests were conducted on breaded cod sticks during refrigerated storage (17 days) at 4 °C, monitoring the pH, microbiological and sensory quality. In addition, the nutritional quality of both the breaded and control samples was assessed. The results highlighted that active samples showed higher phenol and flavonoid content and higher antioxidant activity compared to the control fish, suggesting that pomegranate peel powder was responsible for a significant increase in cod stick nutritional quality. Furthermore, the cod stick active breading led to a delay in microbial growth without affecting the sensory properties; rather, it helped slow down the sensory attribute decline during the refrigerated storage. The data suggest that using pomegranate byproducts in breaded cod stick was effective in prolonging its shelf life, as well as improving its nutritional quality. Therefore, pomegranate peel powder can be considered as a potential resource as natural food preservative.     

Study of the bromide oxidation by bromate in zwitterionic micellar solutions

The redox reaction Br⁻ + BrO₃⁻ has been studied in aqueous zwitterionic micellar solutions of N‐tetradecyl‐N, N‐dimethyl‐3‐ammonio‐1‐propanesulfonate, SB3‐14, and N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate, SB3‐16. A simple expression for the observed rate constant, k_obs, based on the pseudophase model, could explain the influences of changes in the surfactant concentration on k_obs. The kinetic effect of added NaClO₄ on the reaction rate in SB3‐14 micellar solutions has also been studied. They were rationalized by considering the binding of the perchlorate anions to the sulfobetaine micelles and their competition with the reactive bromide ions for the micellar surface. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 388–394, 2000     

Energy migration in novel pH-triggered self-assembled beta-sheet ribbons

Energy migration between tryptophan residues has been experimentally demonstrated in self-assembled peptide tapes. Each peptide contains 11 amino acids with a Trp at position 6. The peptide self-assembly is pH-sensitive and forms amphiphilic tapes, which further stack in ribbons (double tapes) and fibrils in water depending on the concentration. Fluorescence spectra, quenching, and anisotropy experiments showed that when the pH is lowered from 9 to 2, the peptide self-assembly buries the tryptophan in a hydrophobic and restricted environment in the interior of stable ribbons as expected on the basis of the peptide design. These fluorescence data support directly and for the first time the presence of such ribbons which are characterized by a highly packed and stable hydrophobic interior. In common with Trp in many proteins, fluorescence lifetimes are nonexponential, but the average lifetime is shorter at low pH, possibly due to quenching with neighboring Phe residues. Unexpectedly, time-resolved fluorescence anisotropy does not change significantly with self-assembly when in water. In highly viscous sucrose-water mixtures, the anisotropy decay at low pH was largely unchanged compared to that in water, whereas at high pH, the anisotropy decay increased significantly. We concluded that depolarization at low pH was not due to rotational diffusion but mainly due to energy migration between adjacent tryptophan residues. This was supported by a master equation kinetic model of Trp-Trp energy migration, which showed that the simulated and experimental results are in good agreement, although on average only three Trp residues were visited before emission.     

Optimizing Membranes for Osmotic Power Generation

The design of ion-selective membranes is the key towards efficient reverse electrodialysis-based osmotic power conversion. The tradeoff between ion selectivity (output voltage) and ion permeability (output current) in existing porous membranes, however, limits the upgradation of power generation efficiency for practical applications. Thus, we provide the simple guidelines based on fundamentals of ion transport in nanofluidics for promoting osmotic power conversion. In addition, we discuss strategies for optimizing membrane performance through analysis of various material parameters in membrane design, such as pore size, surface charge, pore density, membrane thickness, ion pathway, pore order, and ionic diode effect. Lastly, a perspective on the future directions of membrane design to further maximize the efficiency of osmotic power conversion is outlined.     

Study of the Reaction 2-(p-Nitrophenyl)Ethyl Bromide + OH(-) in Sulfobetaine Aqueous Micellar Solutions in the Presence and Absence of Added Salts

The reaction of dehydrobromination of 2-(p-nitrophenyl)ethyl bromide with hydroxide ions has been studied in aqueous micellar solutions of N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, SB3-14. The kinetic effects of added salts (NaF, NaCl, NaBr, and NaNO(3)) on the reaction rate in SB3-14 aqueous micellar solutions have also been studied. They were rationalized by considering the binding of the anions, which come from the salt, to the sulfobetaine micelles and their competition with the reactive hydroxide ions for the micellar surface. The equilibrium binding constant of the 2-(p-nitrophenyl)ethyl bromide to the sulfobetaine micelles was estimated by recording the changes in the spectra of the organic substrate when the SB3-14 concentration in the micellar medium changed. This value was in agreement with that obtained from fitting of kinetic data. The second-order rate constant in the micellar pseudophase revealed that the reaction is faster in SB3-14 micelles than in water. This acceleration seems independent of the presence of added salts and can be explained by considering that SB3-14 micelles favor reactions in which charge is delocalized in the transition state. Copyright 2001 Academic Press.