A comparison of emulsifiers for the formation of oil-in-water emulsions: stability of the emulsions within 9 h after production and MR signal properties

Objective

To provide a basis for the selection of suitable emulsifiers in oil-in-water emulsions used as tissue analogs for MRI experiments. Three different emulsifiers were investigated with regard to their ability to stabilize tissue-like oil-in-water emulsions. Furthermore, MR signal properties of the emulsifiers themselves and influences on relaxation times and ADC values of the aqueous phase were investigated.

Materials and methods

Polysorbate 60, sodium dodecyl sulfate (SDS) and soy lecithin were used as emulsifiers. MR characteristics of emulsifiers were assessed in aqueous solutions and their function as a stabilizer was examined in oil-in-water emulsions of varying fat content (10, 20, 30, 40, 50%). Stability and homogeneity of the oil-in-water emulsions were evaluated with a delay of 3 h and 9 h after preparation using T₁ mapping and visual control. Signal properties of the emulsifiers were investigated by ¹H-MRS in aqueous emulsifier solutions. Relaxometry and diffusion weighted MRI (DWI) were performed to investigate the effect of various emulsifier concentrations on relaxation times (T₁ and T₂) and ADC values of aqueous solutions.

Results

Emulsions stabilized by polysorbate 60 or soy lecithin were stable and homogeneous across all tested fat fractions. In contrast, emulsions with SDS showed a significantly lower stability and homogeneity. Recorded T₁ maps revealed marked creaming of oil droplets in almost all of the emulsions with SDS. The spectral analysis showed several additional signals for polysorbate and SDS. However, lecithin remained invisible in ¹H-MRS. Relaxometry and DWI revealed different influences of the emulsifiers on water: Polysorbate and SDS showed only minor effects on relaxation times and ADC values of aqueous solutions, whereas lecithin showed a strong decrease in both relaxation times (r_1,lecithin = 0.11 wt.%⁻¹ s⁻¹, r_2,lecithin = 0.57 wt.%⁻¹ s⁻¹) and ADC value (Δ(ADC)_lecithin =  − 0.18 × 10^–3 mm²/s⋅wt.%) with increasing concentration.

Conclusion

Lecithin is suggested as the preferred emulsifier of oil-in-water emulsions in MRI as it shows a high stabilizing ability and remains invisible in MRI experiments. In addition, lecithin is suitable as an alternative means of adjusting relaxation times and ADC values of water.

     

Microcalorimetry for characterization of film formation and cure of coatings and adhesives

A new microcalorimeter with eight parallel channels using robust, low cost sensors for characterization of coatings and adhesives is described and first experiments on coatings and adhesives are presented. The calorimetric sensors are based on thin glass plates (20 mm × 20 mm, thickness 150 μm) with heater and thermocouple sputtered on the surfaces (calorimetric active area of about 9 mm²). The setup allows heating and cooling experiments as well as isothermal measurements in the temperature-modulated mode with up to eight sensors in parallel. The measured quantities are the real (C^′_p) and imaginary part (C^″_p) of the complex heat capacity (), the related absolute value of the heat capacity () and the heat flow . An industrial computer (NI PXI system) with specific software for calibration and data recording controls the electronic components. Sensors can be embedded in a temperature controlled oven (heating and cooling by Peltier elements) or alternatively in a climatic cabinet with controlled temperature and humidity.

The method has been applied successfully to monitoring of film formation of aqueous polymer dispersions (styrene-acrylate copolymer) and curing of coatings.     

Pseudolesions in liver sonography

Two different molecular forms of cholecystokinin (CCK) were studied with respect to their modulatory effect on non-MHC restricted or natural killer (NK) cell cytotoxicity. NK activity of peripheral blood mononuclear cells was found to be hardly affected by co-incubation with either CCK-8 or CCK-33 within a physiological concentration range against K-562 or Caco-2 tumour target cells. NK activity by lamina propria mononuclear cells isolated from histologically normal intestinal mucosa was found to be enhanced dose-dependently by incubation with CCK-8 in the 4-h assay against K-562, but not in the prolonged 18-h assay or against Caco-2 targets. In contrast, CCK-8 showed a tendency to inhibit NK activity in the prolonged 18-h assay against K-562; however, these alterations were not found to be statistically significant. CCK-33 was not found to modulate the NK activity of lamina propria mononuclear cells. It is suggested that NK activity by lamina propria mononuclear cells may be stimulated preferentially by CCK-8 because this molecular form of CCK in particular predominates in the nervous tissue of the intestinal mucosa.     

Micelle formation in mixtures of nonionic and cationic detergents

The effect of a homologous series of polyoxyethylene n-dodecanols on the critical micelle concentration (cmc) of mixtures with n-dodecyl trimethyl ammonium bromide (DTAB) and of polyoxyethylene n-hexadecanols on the cmc of mixtures with n-hexadecyl trimethyl ammonium bromide (CTAB) has been studied in terms of the composition of the mixtures. The cmc of the nonionic component of the mixed micelles is approximately one hundredth of that of the cationic component. Only a gradual increase in the cmc values of the mixed micelles above the values of the nonionic components was observed in the composition range of 0–75 mole % or 0–90 mole %, respectively, of cationic detergent. This is followed by an abrupt transition to the high cmc values of the cationic component. This abrupt transition is considerably reduced by addition of NaBr. It is postulated that in the absence of added electrolyte the degree of ionic repulsion of the cationic component in mixed micelles is markedly decreased as the proportion of nonionic component reaches a threshold range of 25 or 10 mole %, respectively. Swamping of charges reduces ionic repulsion in NaBr solutions and, consequently, the abrupt transition in the cmc vs. composition curves is reduced.     

Signal losses in diffusion preparation: Comparison between spin-echo, stimulated echo and SEASON

Diffusion-weighted magnetic resonance imaging and spectroscopy commonly apply a spin-echo or stimulated echo preparation including sensitizing field gradients. The article reports on a systematic numerical approach to an optimum diffusion preparation considering undesired signal losses caused by relaxation. A large range of possible applications on whole-body units and animal scanners is covered. Instructions for an optimized type and timing of the diffusion preparation are provided for the readership, based on the desired diffusion weighting (b-value), the available maximum field gradient amplitudes, the RF pulse durations and gradient ramp times, and the relaxation characteristics of the specimen (or tissue) of interest. In addition, a new type of diffusion preparation named SEASON (simultaneous Spin-Echo And Stimulated echO preparatioN) is introduced and compared with spin-echo and stimulated echo diffusion preparation. It is demonstrated that spin-echo preparation is superior to stimulated echo preparation in all cases with T₂ ≈ T₁ and in all cases with relatively low diffusion weighting resulting in short duration of diffusion sensitizing gradients δ « T₂. For tissues with T₂ « T₁ (as musculature or red bone marrow) stimulated echo preparation becomes superior to spin-echo preparation for high ratios b/A² (b-value indicates diffusion weighting,A is the maximum gradient amplitude). The new SEASON technique allows a higher yield in signal intensity compared to spin-echo or stimulated echo preparations in clinically relevant cases. © 1998 Elsevier Science B.V. All rights reserved.     

Ultrafast thermal processing and nanocalorimetry at heating and cooling rates up to 1 MK/s

To generate artificial materials with advanced physical and chemical properties and to study phase transition kinetics on submillisecond time scale, an ultrafast nonadiabatic membrane nanocalorimeter was constructed. A set of commercially available membrane gauges for ultrafast nanocalorimetry has been developed. The gauges placed in a thermostat with controlled helium gas pressure and temperature can be utilized as devices for thermal processing and calorimetry with resolution of 1 nJ/K. Controlled ultrafast cooling, as well as heating, up to 10(6) K/s can be attained for nanogram samples. The maximum cooling rate is inversely proportional to the radius of the heated region of the gauge, which was in the range of 10-100 microm depending on the gauge. The minimum addenda heat capacity was 3 nJ/K. The dynamic heat-transfer problem for the temperature distribution in the membrane-gas system at ultrafast processing has been solved. The characteristic rate R(0) corresponding to quasistatic limit of the temperature change in the membrane-gas system has been found to be equal to 10(5) K/s for a 1 microm thick silicon nitride membrane in helium gas. Calorimeter performance at ultrafast rates has been verified by a set of test experiments. The method was applied for thermal processing and calorimetric measurements in a set of linear polymers. It has been established that nearly amorphous polyethylene can be obtained at a cooling rate of 10(6) K/s.     

Solvus Composition Paths in Multicomponent Alloys—Experimental Approach and Correlation with Calphad Calculations for the Example Al–Mg–Si

An experimental approach employing temperature and concentration gradients is presented that is suitable for determining a sequence of solvus concentrations in a single experimental cycle. The Al–Mg–Si system is used as an example. Al solid solutions (“(Al)”) with different compositions and Mg₂Si precipitates were equilibrated in the temperature range between 350 and 550 °C. The equilibrium compositions of (Al) were measured by energy dispersive X‐ray spectroscopy in the transmission electron microscope. The coupled temperature‐concentration values represent a path on the ternary solvus surface. Calphad calculations using different thermodynamic data sets were carried out to relate the experimental results to phase diagram evaluations. The measured solvus path agrees well with solvus data calculated with most recent thermodynamic parameter sets. The experimental approach can be applied to multicomponent alloys irrespective of their number of components with the same experimental effort. The efficiently generated solubility data are suitable to support phase diagram evaluations of multicomponent systems by the Calphad method.     

Social network architecture and the maintenance of deleterious cultural traits

How have changes in communications technology affected the way that misinformation spreads through a population and persists? To what extent do differences in the architecture of social networks affect the spread of misinformation, relative to the rates and rules by which individuals transmit or eliminate different pieces of information (cultural traits)? Here, we use analytical models and individual-based simulations to study how a ‘cultural load’ of misinformation can be maintained in a population under a balance between social transmission and selective elimination of cultural traits with low intrinsic value. While considerable research has explored how network architecture affects percolation processes, we find that the relative rates at which individuals transmit or eliminate traits can have much more profound impacts on the cultural load than differences in network architecture. In particular, the cultural load is insensitive to correlations between an individual''s network degree and rate of elimination when these quantities vary among individuals. Taken together, these results suggest that changes in communications technology may have influenced cultural evolution more strongly through changes in the amount of information flow, rather than the details of who is connected to whom.     

Solid-state reorganization,melting and melt-recrystallization of conformationally disordered crystals (α′-phase) of poly (l-lactic acid)

Conformationally disordered α′-crystals of poly (l-lactic acid) were formed by crystallization of the melt at high supercooling at 95 °C. Analysis of their melting temperature as a function of the crystallinity revealed absence of crystal thickening during isothermal crystallization. Annealing of α′-crystals between the crystallization temperature of 95 °C and their zero-entropy production melting temperature of 150 °C leads to their stabilization, mainly by solid-state reorganization. Heating faster than 30 K s⁻¹ suppresses reorganization and permits superheating of the α′-phase. Consequently, isothermal melting followed by melt-recrystallization becomes accessible. Melting is completed within few hundreds of milliseconds, and melt-recrystallization is about two orders of magnitude faster than crystallization of the isotropic melt at identical temperature. The time required for melting decreases with superheating and increases with the lateral dimension of the lamellar crystals. Laterally extended lamellae require long time for melting of the outer crystal layers, which allows stabilization of the central crystal part. These crystal remnants then serve as seed for immediate recrystallization. In case of complete melting of smaller lamellae, melt-recrystallization is retarded but still distinctly faster than cold- and melt-crystallization, due to incomplete isotropization of the melt.     

The diastereofacial selectivity of the addition of various 1-metalated 1-heptynes to substituted cyclopentanecarbaldehydes. – The use of 1-titanated 1-heptyne for the construction of the alkyl side chain of Prostaglandins

A highly diastereoselective addition of 1-heptyne to substituted cyclopentanecarbaldehydes is one of the indispensable prerequisites to the construction of the (S)-3-hydroxy-1(E)-octenyl side chain of prostaglandins by palladium(II)-catalyzed [3,3]-sigmatropic rearrangement of allylic acetates. It was found that 1-titanated 1-heptynes afford the Cram product at best with a diastereofacial selectivity of 92.5%. The corresponding lithium and magnesium compounds are less diastereoselective.