Aggregation behavior and catalytic activity of systems based on calix[4]resorcinarene derivatives and surfactants. 1. Mixed micellization of aminomethylated calix[4]resorcinarenes with cetyltrimethylammonium bromide in aqueous dimethylformamide

Mixed micellization of amphiphilic aminomethylated calix[4]resorcinarenes and phenols, which are their structural units, with the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous 10—70 vol % DMF decreases the critical micelle concentration; the resulting aggregates are larger than those in the CTAB—DMF—water systems. The micellization of CTAB with aminomethylated calix[4]resorcinarenes proceeds in two steps, while its micellization with phenols is a single-step process. The micellization characteristics depend on the structure and hydrophobicity of the amphiphilic compound and the concentration of DMF.     

Peculiarities in the Water Adsorption and Morphology of Carbon Chars Assessed by NMR

Proton spin-lattice relaxation and (1)H NMR spectroscopic data are used for studies of the water adsorption and morphology of several newly synthesized carbon-based chars. Two NMR lines have been observed in accordance with a difference between macropore and micropore water in a system with heterogeneous pore structure. The macropores occupy about the half of the char particle volume. In aqueous suspension fast molecular exchange between water in macropores and bulk water leads to an intense NMR line with a single spin-lattice relaxation time T(1), which exhibits a strong particle size effect. This effect has been used for the estimation of T(1) of water molecules in the vicinity of paramagnetic centers at the surface of chars, as well as for macropore size estimation. The kinetics of water vapor adsorption in chars as seen by (1)H NMR indicates that this process begins in micropores, which serve as primary adsorption centers. Water molecules in micropores exhibit specific properties which are characteristic of liquids in a small, restricted space, and they give rise to the observed accumulation as well as saturation effects. Copyright 2001 Academic Press.     

Catalytic properties of microheterogeneous systems based on cationic surfactants in transesterification processes

The kinetic parameters of the transesterification processes of carboxylic acid esters under the action of alkylphenolates in aqueous micellar solutions of cetyltrimethylammonium bromide (CTAB) are found. The observed catalytic effect is due to a complex mechanism of the solvent effect, which includes a shift of acid-base equilibria in the nucleophile and the formation of mixed CTAB/alkylphenol micelles. The dynamic structure of these aggregates (size, diffusion mobility, and molecular packing density in a surface layer) has been characterized by spin-probe EPR spectroscopy and high-resolution pulsed-field gradient ¹H NMR spectroscopy.     

Gapped pulses for frequency-swept MRI

A recently introduced method called SWIFT (SWeep Imaging with Fourier Transform) is a fundamentally different approach to MRI which is particularly well suited to imaging objects with extremely fast spin–spin relaxation rates. The method exploits a frequency-swept excitation pulse and virtually simultaneous signal acquisition in a time-shared mode. Correlation of the spin system response with the excitation pulse function is used to extract the signals of interest. With SWIFT, image quality is highly dependent on producing uniform and broadband spin excitation. These requirements are satisfied by using frequency-modulated pulses belonging to the hyperbolic secant family (HSn pulses). This article describes the experimental steps needed to properly implement HSn pulses in SWIFT. In addition, properties of HSn pulses in the rapid passage, linear region are investigated, followed by an analysis of the pulses after inserting the “gaps” needed for time-shared excitation and acquisition. Finally, compact expressions are presented to estimate the amplitude and flip angle of the HSn pulses, as well as the relative energy deposited by the SWIFT sequence.     

Self-diffusion in microemulsions and micellar size

Self-diffusion of all components of two different microemulsions have been measured. Application of Stokes-Einstein equations for surfactant and oil gives a simple relation connecting their size and self-diffusion coefficients. Using the measured self-diffusion coefficients and dimensions of oil molecules known from elsewhere, the size of the surfactant droplets was estimated. This approach turns out to be advantageous in practical determination of droplet size in microemulsions.     

Measuring protein self-diffusion in protein-protein mixtures using a pulsed gradient spin-echo technique with WATERGATE and isotope filtering

Here we report a modified pulsed gradient spin-echo (PGSTE) pulse sequence to measure diffusion coefficients. This approach incorporates WATERGATE combined with isotopic filtering into a standard PGSTE experiment. Doing this eliminates much of the disadvantages from the combination of diffusion encoding and heteronuclear selection intervals and allows for facile modification of the diffusion pulse sequence with flexibility of the time period between RF pulses. The new diffusion pulse sequence is demonstrated using an 15N-labeled peptide and an 15N-labeled protein in a mixture with a protein of similar size.     

Fast and quiet MRI using a swept radiofrequency

A novel fast and quiet method of magnetic resonance imaging (MRI) is introduced which creates new opportunities for imaging in medicine and materials science. The method is called SWIFT, sweep imaging with Fourier transformation. In SWIFT, time-domain signals are acquired in a time-shared manner during a swept radiofrequency excitation of the nuclear spins. With negligible time between excitation and signal acquisition, new possibilities exist for imaging objects consisting of spins with extremely fast transverse relaxation rates, such as macromolecules, semi-solids, and quadrupolar nuclei. The field gradient used for spatial-encoding is not pulsed on and off, but rather is stepped in orientation in an incremental manner, which results in low acoustic noise. This unique acquisition method is expected to be relatively insensitive to sample motion, which is important for imaging live objects. Additionally, the frequency-swept excitation distributes the signal energy in time and thus dynamic range requirements for proper signal digitization are reduced compared with conventional MRI. For demonstration, images of a plastic object and cortical bone are shown.