Tetrabutylammonium alkyl carboxylate surfactants in aqueous solution: self-association behavior, solution nanostructure, and comparison with tetrabutylammonium alkyl sulfate surfactants

A series of long and ultralong chain tetrabutylammonium alkyl carboxylate (TBACm, TBA = tetrabutylammonium ion; Cm = carboxylate ion C(m-1)H(2)(m-1)CO(2)(-) of total carbon number m) surfactants have been obtained by direct neutralization of the fatty acids with m = 12, 14, 18, 22, and 24 by tetrabutylammonium hydroxide. Time-resolved fluorescence quenching has been used to determine the micelle aggregation number (N) of the surfactants with m = 12, 14, and 18 in the temperature range 10-50 degrees C and of the surfactants with m = 22 and 24 in the temperature range 25-60 degrees C. In all instances the values of N were well below those that can be calculated for the maximum spherical micelle formed by surfactants with the same alkyl chain as the investigated surfactants on the basis of the oil drop model for the micelle core. The microstructure of selected solutions of TBAC22 was examined using transmission electron microscopy at cryogenic temperature and compared to the microstructure of solutions of TBA dodecyl and tetradecyl sulfates. These observations generally confirmed the findings of TRFQ. The self-association behavior of these anionic surfactants with TBA counterions is explained on the basis of the large size and the hydrophobicity of the tetrabutylammonium ions. The important differences in behavior that have been evidenced between tetrabutylammonium alkyl carboxylates and alkyl sulfates are discussed in terms of differences in distribution of the surfactant electrical charge on the headgroup and alkyl chain predicted by quantum chemical calculations (Langmuir 1999, 15, 7546).     

In vivo effects of porphyrins on bacterial DNA.

The DNA damage in intact Staphylococcus aureus and E. coli cells induced by photosensitized deuteroporphyrin or hemin is described. Treatment of S. aureus cultures with hemin or photosensitized deuteroporphyrin (Dp) caused time-dependent changes in the plasmidial DNA profiles. The major observation was the disappearance of the plasmid supercoiled fraction. The chromosomal DNA was also affected by hemin and by photosensitized Dp, since its degradation products were detected after exposing the bacterial cells to the porphyrin drugs. Photosensitization of E. coli cells, pretreated with Dp and polymyxin B nonapeptide (PMBNP), also resulted in plasmidial damage. No such damage occurred when E. coli cultures were treated with hemin and PMBNP. The above results can be tightly correlated with the antimicrobial action of porphyrins. Their damage to the bacterial DNA seems to reflect one of the in vivo effects of these porphyrins.     

Photosensitizer–Antibiotic Conjugates: A Novel Class of Antibacterial Molecules

Bacterial resistance to a variety of antibiotics has led to intensive research into the effect of photosensitizers as a cytotoxic agent against bacterial cells. In this study, we synthesized the following conjugates with or without a linker: rose bengal-penicillanic acid (RBPA), rose bengal-linker-penicillanic acid (RBLPA) and rose bengal-linker-kanamycin (RBLKAN). The antibacterial activity of these conjugates was examined on Staphylococcus aureus and Escherichia coli. Exposure of the cultures to 100 J cm⁻² showed that the minimum inhibitory concentration (MIC) of RBPA, RBLPA and RBLKAN on S. aureus was 0.195, 0.156 and 0.004 μm, respectively. The MIC of RBPA, RBLPA and RBLKAN on E. coli was 1.56, 2.5 and 0.156 μm, respectively. In dark control experiments, the MIC of these conjugates was not detected until a concentration that was 16-fold that of the MIC found in the light experiments. RBPA and RBLPA as well as RBLKAN are bactericidal for both bacterial cells. Total eradication of S. aureus and E. coli was observed with RBLKAN (0.078 and 20 μm 16 J cm⁻², respectively). Under these conditions, scanning electron microscopic analysis showed significant damage to these bacteria. However, the photosensitizer and antibiotics individually were not effective.     

Influence of hydrocarbon surfactant on the aggregation behavior of silicone surfactant: observation of intermediate structures in the vesicle-micelle transition

Intermediate structures of the aggregates in the aqueous solution of an ABA-type silicone surfactant and in the process of an SDS-induced vesicle-micelle transition are reported. In single ABA silicone surfactant aqueous solutions, large multilamellar vesicles (MLV), small single lamellar vesicles (SLV), threadlike micelles (TLM), and spheroidal micelles were observed. Interestingly, a large amount of TLMs were found entrapped into the large MLVs, but not in SLVs. Disintegration of the small vesicles inside the MLVs indicates that the entrapped TLM are from the disintegrated membrane of the entrapped small vesicles. Addition of SDS induced a transition from vesicles or threadlike micelles to spheroidal micelles. The intermediate structures, such as the appearance of small holes in the vesicle membrane, the budding of threadlike micelles from the membrane fracture, and the clusters of spheroidal micelles, were observed with increase of the SDS concentration. The electrical conductivity measurements indicated that complex micelles of SDS and silicone surfactant were formed in the solution due to the interaction between the SDS and PEO part of the silicone surfactant.     

Mechanism of collision-induced intersystem crossing in CO

We have studied inert-gas pressure effects on the fluorescence decay in CO selectively excited to the υ = 0 to 7 vibronic levels of the A ¹Π electronic state. It is shown that the dependence of the quenching cross section σ_isc on the average value of the ST mixing coefficient (β²) has a quasi-logarithmic form. A simple two-level model describing semiquantitatively this behavior is proposed.     

SPECTROSCOPY AND PHOTOSENSITIZATION OF SAPPHYRINS IN SOLUTIONS AND BIOLOGICAL MEMBRANES

Abstract A spectroscopic and photophysical study of three new sapphyrin molecules is presented. The sapphyrin backbone that was derivatized to make them water soluble possesses an absorption band around 700 nm, a desired property for biological photosensitization. We studied the absorption and fluorescence spectra, from which evidence for aggregation in solvents of different polarities was obtained. The extent of aggregation is correlated with the nature of the attached moiety. The absolute quantum yields of singlet oxygen production were measured, with 1,3-diphenyl isobenzofuran as a model target, and were 0.13–0.18 in ethanol. The binding constants to liposomes and to cells were determined spectroscopically and were found to correspond to the hydrophobicities of the compounds, with an additional effect, ascribed to the sugar moiety, which was found in the case of one of the sapphyrins. The efficiency of photodamage to Staphylococcus aureus by sapphyrins and hematoporphyrin was equivalent, on the basis of cells killed per microgram of sensitizer in the incubation mixture.     

Spin-boson thermal rectifier

Rectification of heat transfer in nanodevices can be realized by combining the system inherent anharmonicity with structural asymmetry. We analyze this phenomenon within the simplest anharmonic system-a spin-boson nanojunction model. We consider two variants of the model that yield, for the first time, analytical solutions: a linear separable model in which the heat reservoirs contribute additively, and a nonseparable model suitable for a stronger system-bath interaction. Both models show asymmetric (rectifying) heat conduction when the couplings to the heat reservoirs are different.     

Extreme accumulation layers on ZnO surfaces due to He+ ions

Accumulation layers with excess surface electron densities of up to 10¹⁴ cm^?2 have been produced on the (001) face of ZnO single crystals by an electrical discharge in helium atmosphere. Hall effect measurements show that at these extreme surface electron densities both the electron density and the mobility are temperature independent from room temperature down to 1.6 K.     

Molecular wires acting as coherent quantum ratchets

The effect of laser fields on electron transport through a molecular wire weakly coupled to two leads is investigated. The molecular wire acts as a coherent quantum ratchet if the molecule is composed of periodically arranged, asymmetric chemical groups. This setup presents a quantum rectifier with a finite dc response in the absence of a static bias. The nonlinear current is evaluated in closed form within the Floquet basis of the isolated, driven wire. The current response reveals multiple current reversals together with a nonlinear dependence on the amplitude and the frequency of the laser field. The current saturates for long wires at a nonzero value, while it may change sign upon decreasing its length.