Quantitative adiabatic-refocused INEPT (QA-RINEPT) as a tool for fast and reliable characterization of polyols.

13 C nuclear magnetic resonance (NMR) is a powerful tool for the detailed characterization and structure elucidation of polymeric samples. The low natural abundance and sensitivity of the 13 C isotope, however, lead to very long acquisition time, therefore limiting the use of such technique. We report here the implementation of a quantitative method, quantitative adiabatic-refocused insensitive nuclei enhanced by polarization transfer (QA-RINEPT), for the characterization of polyol samples. The method, based on the well-known insensitive nuclei enhanced by polarization transfer sequence, allows the boost in sensitivity of the carbon resonances without sacrificing the quantitative aspects of the analysis. This is achieved controlling the polarization transfer mechanism and introducing a response factor to calculate precisely the sensitivity gain of the different carbon signals. Compared with the standard single pulse quantitative experiment, the QA-RINEPT method produces up to 4.7× signals enhancement per unit of time. An in-depth statistical analysis was conducted to confirm the reliability of the QA-RINEPT method. We show that there is excellent agreement between the new and old 13 C-NMR methods for the quantitative determination of several important polyol properties such as the comonomer and initiator content as well as the ratio of primary and secondary hydroxyl groups.

Effect of molecular exchange on water droplet size analysis as determined by diffusion NMR: The W/O/W double emulsion case.

HYPOTHESIS: The accuracy of the inner water droplet size determination of W/O/W emulsions upon water diffusion measurement by diffusion NMR was evaluated. The resulting droplet size data were compared to the results acquired from the diffusion measurement of a highly water soluble marker compound with low permeability in the oil layer of a W/O/W emulsion, which provide a closer representation of the actual droplet size. Differences in droplet size data obtained from water and the marker were ascribed to extra-droplet water diffusion. EXPERIMENTS: The diffusion data of the tetramethylammonium cation marker were measured using high-resolution pulsed field gradient NMR, whereas the water diffusion was measured using both low-resolution and high-resolution NMR. Different data analysis procedures were evaluated to correct for the effect of extra-droplet water diffusion on the accuracy of water droplet size analysis. FINDINGS: Using the water diffusion data, the use of a low measurement temperature and diffusion delay Δ could reduce the droplet size overestimation resulting from extra-droplet water diffusion, but this undesirable effect was inevitable. Detailed analysis of the diffusion data revealed that the extra-droplet diffusion effect was due to an exchange between the inner water phase and the oil phase, rather than by exchange between the internal and external aqueous phase. A promising data analysis procedure for retrieving reliable size data consisted of the application of Einstein's diffusion law to the experimentally determined diffusion distances. This simple procedure allowed determining the inner water droplet size of W/O/W emulsions upon measurement of water diffusion by low-resolution NMR at or even above room temperature.

Generic applications of (13) C-detected NMR diffusion to formulated systems with suppression of thermal convection induced by proton decoupling.

Fast and effective structural/compositional analysis on formulated systems represents one of the major challenges encountered in analytical science. (13) C-detected diffusion represents a promising tool to tackle the aforementioned challenges, particularly in industry. Toward exploring the generic applications of (13) C-detected diffusion, thermal convection induced by (1) H decoupling has been identified as a key factor that resulted in significantly reduced resolution in the diffusion dimension. Optimization of experimental parameters and utilization of double-stimulated echo-based pulse sequence both can effectively suppress the thermal convection caused by the (1) H decoupling, the success of which allows robust and generic applications of (13) C-detected diffusion to systems from mixtures of small molecules, polymer blends, and copolymers to actual complex formulated systems. The method is particularly powerful in differentiating small molecules from polymers, polymer blends from copolymers, and end-group analysis. Copyright © 2016 John Wiley & Sons, Ltd.

Effect of molecular exchange on water droplet size analysis in W/O emulsions as determined by diffusion NMR.

Using NMR diffusometry, the diffusion of water and tetramethylammonium chloride was recorded in order to determine the water droplet size distribution in W/O emulsions. This study aimed at evaluating the effect of extradroplet diffusion of water on the estimated droplet size distribution upon comparison to the real droplet size distribution. The latter originated from the diffusion behavior of the tetramethylammonium cation (TMA+), which is known to have a much lower permeability through the oil phase as compared to water. Whereas both low-resolution and high-resolution pulsed field gradient NMR revealed that the water droplet size overestimation could be reduced selecting either a lower measurement temperature during diffusion analysis, or a smaller diffusion delay value Δ, still comparison to TMA+ diffusion indicated that artefacts were unavoidable even at low Δ and temperature. In order to correct for this extradroplet water diffusion phenomenon, different data analysis methods were evaluated. The previously described Pfeuffer exchange model could only partly compensate for the effect of extradroplet diffusion on the water droplet size determination. On the other hand, accurate water droplet size analysis results were obtained by correcting the experimentally determined diffusion distances based on Einstein's diffusion law. As such, reliable data could be obtained by low resolution NMR based on water diffusion at or even above room temperature.

Graphene field effect transistors with niobium contacts and asymmetric transfer characteristics.

We fabricate back-gated field effect transistors using niobium electrodes on mechanically exfoliated monolayer graphene and perform electrical characterization in the pressure range from atmospheric down to 10(-4) mbar. We study the effect of room temperature vacuum degassing and report asymmetric transfer characteristics with a resistance plateau in the n-branch. We show that weakly chemisorbed Nb acts as p-dopant on graphene and explain the transistor characteristics by Nb/graphene interaction with unpinned Fermi level at the interface.

NMR investigation of exchange dynamics and binding of phenol and phenolate in DODAC vesicular dispersions.

The interaction between phenol molecules, both in their undissociated and dissociated states, and cationic dioctadecyl dimethylammonium chloride (DODAC) vesicles were thoroughly investigated using NMR techniques. In particular, diffusion and relaxation measurements, combined with the two sites Kärger model, were used to evaluate the exchange dynamics and the binding of the aromatic molecules to the vesicles. The results reveal that, besides concentration and vesicle preparation method, pH conditions have the biggest impact on the phenol sorption behavior. Although the dissociated form of phenol formed at high pH is more hydrophilic, the results indicated that phenol-DODAC interactions were largely favored in basic conditions as a consequence of the strong electrostatic interaction between the phenolate anions and the cationic surfactant headgroup.

Enclosed volume determination of concentrated dioctadecyldimethylammonium chloride (DODAC) vesicular dispersions by low-resolution proton NMR diffusometry and T2 relaxometry.

The enclosed volume of concentrated dioctadecyldimethylammonium chloride (DODAC) dispersions has been determined by means of low-resolution NMR pfg-diffusometry and T(2) relaxometry. The pfg-NMR diffusometry method is based on the different diffusion behaviors of water in the external and internal phases and as such does not require the addition of a tracer. On the other hand, T(2) relaxometry is based on the different relaxation behaviors of water fractions upon addition of manganese chloride as external (paramagnetic) probe. It was noticed that reliable results are found only for temperatures below the phase transition temperature of DODAC, when the exchange between the two water compartments can be neglected. At 5 °C, these two independent methods resulted in similar enclosed volume values, meaning that the results are reliable and reflect the real enclosed volume. In addition, the T(2) relaxometry method has been proven to be useful in the investigation of the DODAC membrane permeability.

Quantification of hydrophilic ethoxylates in polysorbate surfactants using diffusion H1 NMR spectroscopy.

Polysorbate surfactants (commercially available as Tween) are widely used in pharmaceutical, cosmetic and food products. They are generally considered as esters of ethoxylated sorbitan with fatty acids. Diffusion H1 NMR spectroscopy on a solution of polysorbate 20 in D2O revealed that only one diffusion coefficient was found for the fatty acyl part. Using the Stokes-Einstein equation, it became obvious that this diffusion behavior was caused by micelles. On the other hand, two significantly different diffusion coefficients were found for the methylene groups of ethylene oxide (EO). This indicates the presence of two distinct EO containing species in solution. Since the slowest diffusing EO species has the same diffusion coefficient as the fatty acyl part, it corresponds to the micellar (i.e. fatty acyl bound) ethoxylates. The diffusion coefficient of the fastest diffusing EO species was a factor of four larger than that of the slowly diffusing species and was attributed to water-soluble non-esterified ethoxylates. A solution of polysorbate 20 in the presence of NaOD was prepared to investigate if hydrolysis of the sorbitan ester could be the reason for the occurence of these hydrophilic ethoxylates. It was found that alkaline hydrolysis does lead to an increasing fraction of non-esterified ethoxylates, but is not the cause of its presence in untreated polysorbate samples since these species were also found in solutions of polyethylene glycol oleyl ether (commercially available as Brij), which are not susceptible to hydrolysis. Fractionation of the EO species present in polysorbate 20 into an amphiphilic and a hydrophilic fraction was only partly obtained by activated carbon adsorption. On the other hand, sequential extraction of aqueous polysorbate solutions by ethyl acetate and chloroform enabled a nearly complete fractionation. H1 NMR spectroscopy proved to be very useful since it allows in situ determination of the global composition of a surfactant sample, as well as quantification of both the amphiphilic and hydrophilic ethoxylate fractions via diffusion measurements.