NMR-investigation of restricted self-diffusion of oil in rape seeds

The self-diffusion of oil and water in rape seeds (Brassica napus L.) was measured with the NMR pulsed field gradient technique. The self-diffusion of oil was found to be completely restricted for diffusion times > 30 ms. The experiments could be explained in terms of the model of diffusion within spherical droplets and a Gaussian mass distribution of the droplet radii. The mean droplet radius was found to be about 0.7 m; this value decreased somewhat with increasing moisture content of the seeds. The experiments could also be explained with a Gaussian number distribution of droplet radii and a fraction of immobile protons in the NMR signal of 5 ... 10%, possibly arising from lipid protons. Though the transverse nuclear magnetic relaxation decay of the oil protons is not a single exponential we observe one uniform diffusive mobility for the oil molecules. The water self-diffusion coefficient at maximum moisture content of about 40% was determined to be 4.2 · 10^-10 m² s^-1 which is typical for swollen polymer-solvent systems at such a concentration. Offprint requests to: P. W. Kuchel     

PFG-NMR measurements of the self-diffusion coefficients of water in equilibrium poly(HEMA-co-THFMA) hydrogels

The self-diffusion coefficients for water in a series of copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA, swollen with water to their equilibrium states have been studied at 310 K using PFG-NMR. The self-diffusion coefficients calculated from the Stejskal-Tanner equation, D(obs), for all of the hydrated polymers were found to be dependent on the NMR storage time, as a result of spin exchange between the proton reservoirs of the water and the polymers, reaching an equilibrium plateau value at long storage times. The true values of the diffusion coefficients were calculated from the values of D(obs) in the plateau regions by applying a correction for the fraction of water protons present, obtained from the equilibrium water contents of the gels. The true self-diffusion coefficient for water in polyHEMA obtained at 310 K by this method was 5.5 x 10(-10) m(2)s-1. For the copolymers containing 20% HEMA or more a single value of the self-diffusion coefficient was found, which was somewhat larger than the corresponding values obtained for the macroscopic diffusion coefficient from sorption measurements. For polyTHFMA and copolymers containing less than 20% HEMA, the PFG-NMR stimulated echo attenuation decay curves and the log-attenuation plots were characteristic of the presence of two diffusing water species. The self-diffusion coefficients of water in the equilibrium-hydrated copolymers were found to be dependent on the copolymer composition, decreasing with increasing THFMA content.     

Permeability of lysozyme tetragonal crystals to water

Diffusion of water within cross-linked tetragonal crystals of hen egg-white lysozyme has been measured and simulated on a computer using the X-ray structure of water-filled channels within the crystal lattice. Relative to the self-diffusion coefficient of bulk water molecules, the experimental diffusion coefficient of water within the crystal was found to be 13 times reduced in the (001) crystallographic plane and 5 times reduced in the [001] direction. Comparison of the experimental and computer simulated diffusion coefficients shows that steric limitations for water diffusion are mostly responsible for this reduction of the water diffusion in the crystal, with the self-diffusion coefficient of intracrystalline water reduced by no more than 30–40% as compared to that of bulk water.     

Self-diffusion of polymers in cartilage as studied by pulsed field gradient NMR

Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) was used to investigate the self-diffusion behaviour of polymers in cartilage. Polyethylene glycol and dextran with different molecular weights and in different concentrations were used as model compounds to mimic the diffusion behaviour of metabolites of cartilage. The polymer self-diffusion depends extremely on the observation time: The short-time self-diffusion coefficients (diffusion time Delta approximately 15 ms) are subjected to a rather non-specific obstruction effect that depends mainly on the molecular weights of the applied polymers as well as on the water content of the cartilage. The observed self-diffusion coefficients decrease with increasing molecular weights of the polymers and with a decreasing water content of the cartilage. In contrast, the long-time self-diffusion coefficients of the polymers in cartilage (diffusion time Delta approximately 600 ms) reflect the structural properties of the tissue. Measurements at different water contents, different molecular weights of the polymers and varying observation times suggest that primarily the collagenous network of cartilage but also the entanglements of the polymer chains themselves are responsible for the observed restricted diffusion. Additionally, anomalous restricted diffusion was shown to occur already in concentrated polymer solutions.     

表面活性剂对链霉素在内蒙古牧区土壤中吸附解吸的影响

通过静态吸附实验,研究了3种不同类型的表面活性剂(阳离子:十六烷基三甲基溴化铵,CTAB;阴离子:十二烷基苯磺酸钠,SDBS;非离子,曲拉通100,TX-100)对链霉素(Streptomycin,STR)在内蒙古牧区土壤中吸附解吸的影响。结果表明,3种表面活性剂的存在均会增加STR在土壤中吸附的线性程度。CTAB的存在抑制了STR在土壤表面的吸附同时抑制了STR的解吸,然而SDBS的存在降低了STR在土壤中的吸附量并增加了吸附过程的可逆性。与CTAB和SDBS不同,TX-100对STR在土壤中的吸附的影响取决于其添加浓度。低浓度的TX-100对STR的吸附促进作用大于高浓度。随着TX-100浓度的增加,TX-100对STR的增溶作用加剧。促使吸附在土壤表面的STR迁移到水相中,从而抑制了STR的吸附,进而促进了STR的解吸。     

Analysis of diffusion and relaxation behavior of water in apple parenchymal cells

It has been demonstrated by an example of apple parenchymal cells that NMR spectroscopy can be used to analyze the relaxation and diffusion of water molecules in plant cells. With small diffusion times, three relaxation components have been distinguished, which correspond to water in a vacuole, in the cytoplasm, and in intercellular liquid. The coefficient of self-diffusion corresponding to these components have been determined. With large diffusion times, it is possible to distinguish two components. For the slowly relaxing component (which corresponds to water in a vacuole), the regime of restricted diffusion was observed. For a quickly relaxing component, an anomalous increase in the coefficient of self-diffusion with the time of diffusion took place.     

NMR imaging of the diffusion of water at 310 K into semi-IPNs of PEM and poly(HEMA-co-THFMA) with and without chlorhexidine diacetate

Magnetic resonance imaging has been used to monitor the diffusion of water at 310 K into a series of semi-IPNs of poly(ethyl methacrylate), PEM, and copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA. The diffusion was found to be well described by a Fickian kinetic model in the early stages of the water sorption process, and the diffusion coefficients were found to be slightly smaller than those for the copolymers of HEMA and THFMA, P(HEMA-co-THFMA), containing the same mole fraction of HEMA in the matrix. A second stage sorption process was identified in the later stage of water sorption by the PEM/PTHFMA semi-IPN and for the systems containing a P(HEMA-co-THFMA) component with a mole fraction HEMA of 0.6 or less. This was characterized by the presence of water near the surface of the cylinders with a longer NMR T(2) relaxation time, which would be characteristic of mobile water, such as water present in large pores or surface fissures. The presence of the drug chlorhexidine in the polymer matrixes at a concentration of 5.625 wt % was found not to modify the properties significantly, but the diffusion coefficients for the water sorption were systematically smaller when the drug was present.     

Water sorption studies of hybrid biofiber-reinforced natural rubber biocomposites

Hybrid biofibers (sisal and oil palm) were incorporated into natural rubber matrix. The water absorption characteristics of the composites were evaluated with reference to fiber loading. The influence of temperature on water sorption of the composites is also analyzed. Moisture uptake was found to be dependent on the properties of the biofibers. The mechanism of diffusion in the gum sample was found to be Fickian in nature, while in the loaded composites, it was non-Fickian. Sisal and oil palm fibers were subjected to different treatments such as mercerization and silanation. The effect of chemical modification on moisture uptake was also analyzed. Chemical modification was seen to decrease the water uptake in the composites. The thermodynamic parameters of the sorption process were also evaluated. Activation energy was found to be maximum for the gum sample.     

Calculation of self-diffusion coefficients of the [BMIM][TFSA]/water system by molecular dynamics simulation

We performed a molecular dynamics simulation to calculate the self-diffusion coefficients of 1-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and water in a water–ionic liquid mixture. We then compared the simulated self-diffusion coefficients of cation, anion and water molecules with experimental data and with simulated data from the literature. Although the simulation overestimated the self-diffusion coefficients of ions, the simulated results qualitatively reproduced the enhancement of the self-diffusion coefficients of water as the water molar fraction increased. We also calculated the radial distribution functions to investigate the solution structure, i.e. the clustering of water molecules. The clustering of water in ionic liquid was found to play an important role in the enhancement of the diffusion of water molecules in the ionic liquid.     

Relationship between Recrystallization Rate of Ice Crystals in Sugar Solutions and Water Mobility in Freeze-Concentrated Matrix

To better understand the relation between recrystallization rate and water mobility in freeze-concentrated matrix, isothermal ice recrystallization rates in several sugar aqueous solutions and self-diffusion coefficients of water component in corresponding freeze-concentrated matrix were measured. The sugars used were fructose, glucose, maltose, and sucrose. The sugar concentrations and temperature were varied so that ice contents for all samples were almost equal. Neither recrystallization rates nor diffusion coefficients depended uniformly on temperature. The recrystallization rates increased with increasing the diffusion coefficients, and a direct relationship was found between recrystallization rate and diffusion coefficient. This indicated that self-diffusion coefficient of water component in freeze-concentrated matrix is a useful parameter for predicting and controlling recrystallization rate in sugar solutions relevant to frozen desserts.     

Effects of Cosolvent and Temperature on the Desorption of Polynuclear Aromatic Hydrocarbons from Contaminated Sediments of Chien-Jen River,Taiwan

This study evaluated the effects of the water-miscible cosolvent and temperature on the sorption-desorption of polynuclear aromatic hydrocarbons (PAHs) from contaminated sediments in Chien-Jen River, Taiwan. Sediment samples from five sampling stations of downstream section were utilized in this study. Phenanthrene and anthracene were selected as target compounds. The cosolvent effect on sorption of phenanthrene and anthracene was examined by the addition of various volume fractions of methanol (i.e., 0.3, 0.5, 0.7, and 0.9, respectively) in the sediment/water systems. The utility of the log-linear cosolvency model for predicting PAH sorption from solvent mixtures was evaluated. An inverse relationship was observed for sorption coefficients of phenanthrene and anthracene as a function of increasing cosolvent. The effect of temperature on sorption of phenanthrene and anthracene was conducted at temperature from 10°C to 40°C. The use of elevated temperatures in desorption experiments increased the PAH release from sediments. It was observed that sorption of phenanthrene and anthracene onto sediments decreased when temperature increased. The decrease of sorption coefficient of phenanthrene was more sensitive than that of anthracene. The magnitude of decreased sorption was attributed by the increased desorption rate constant, solubility, and heterogeneities of sediments.     

Nonexponential Diffusion Extinction of Spin Echo from Water Protons in Wheat Root

The method of NMR spin echo with the magnetic field pulse gradient was used for studying self-diffusion of water molecules in the radial root direction. It was shown on the basis of physiologopharmacological methods of modification of the object that the coefficients of water self-diffusion resulting from computer decomposition of nonexponential diffusion extinction of the relative echo amplitude in the root to components are related to the subcellular and supercellular organization (structure) of the root and reflect changes in water permeability of the two transport channels of plasmodesmas.     

Pesticide desorption from soils facilitated by dissolved organic matter coming from composts: experimental data and modelling approach

Dissolved organic matter (DOM) interaction with pesticides was examined studying the ability of DOM to desorb 8 pesticides previously sorbed to soil. DOM was originating from municipal waste composts at two maturity degrees, recovered at 20°C and by hot-pressurised subcritical water. Pesticide desorption depended on their previous sorption on soil. When sorption was low (K_OC ≤ 50, sulcotrione, metalaxyl), water was more efficient than DOM for desorption. On the contrary, when sorption was high (K_OC ≥ 2000, trifluraline), little effect of DOM was observed. For the moderately sorbed pesticides, DOM favoured pesticide desorption compared to water. For the lowest sorbed pesticides (K_OC ≤ 100), hysteresis was increased with larger proportions of DOM extracted with subcritical-water. Dissolved organic matter extracted from fresh-immature compost had larger capacity to mobilize the sorbed pesticides than the DOM from the mature compost. The pesticide desorption resulted from the positive and competitive interactions between pesticide, DOM and soil surfaces. These interactions were modelled considering separate partitioning coefficients. A general equation allowed the deduction of specific coefficients describing interactions in solution between pesticides and the non-sorbed fraction of DOM remaining in solution. This fraction was supposed to contain the most hydrophilic fraction of DOM and was able to interact with the most polar pesticide (amitrol). When pesticide hydrophobicity increased, the partitioning between pesticide and DOM decreased. Modelling the three-phase system (liquid, DOM and solid phases) pointed out that the solid phase played the most important role on pesticide behaviour through the sorption process of DOM and pesticides.     

Bioavailability of Sorbed 3-Chlorodibenzofuran

One of the main factors impeding the bioremediation of polluted soils, sediments, and aquifers is the low bioavailability of chemicals which are sorbed by organic matter. To obtain more insight into the factors that control the degradation of sorbed compounds, we used a defined model system in which 3-chlorodibenzofuran (3CDF) was the organic contaminant, porous Teflon granules were the sorbent, and Sphingomonas sp. strain HH19k was the test organism. The sorption of 3CDF to Teflon reached equilibrium within 150 min. The curved shape of the sorption isotherm, the extent of sorption, and the desorption kinetics suggested that there was a surface interaction (adsorption) between 3CDF and Teflon which took place mainly inside the pores of the granules. The kinetics of desorption could be ascribed to sorption-retarded radial diffusion inside the granules since the desorption rate not only was correlated with the sorbed-phase concentration, but also depended on the equilibration status of sorption, since (i) the high initial desorption rate sharply declined because of the depletion of 3CDF in the outermost parts of the granules, but high rates were observed again after the system had been given time to reequilibrate, and (ii) the initial desorption rate was higher when the preceding contact time between sorbate and sorbent was shorter (i.e., most 3CDF was still located in the exterior parts of the granules). These characteristics were observed irrespective of whether the desorption was driven by percolating water through the sorbent or by attaching active bacteria to the sorbent. 3CDF consumption by attached cells drove 3CDF desorption to a considerable extent. The attached cells were thus efficiently supplied with desorbing 3CDF. On the basis of our results, we propose that the rate at which a sorbed substrate becomes available for organisms is influenced by (i) the specific affinity of the degrading organisms (i.e., their ability to reduce the aqueous substrate concentration) and (ii) the tendency of the organisms to adhere to the sorbent.     

The diffusion of gibberellins into agar and water during early germination of Pharbitis nil Choisy

Agar diffusion of imbibed seeds yielded significant amounts of diffusible Gibberellin-like substances. An analysis of the extractable and diffusible gibberellin-like substance, including an analysis of the remaining imbibition water of the seeds, indicated that a significant part of these gibberellin-like substances could be attributed to a net biosynthesis of these substances in the imbibing seeds. At the same time it was found that water diffusion yielded considerably more gibberellin-like activities than comparable agar diffusions i.e. 10 to 12 fold in general.Agar as well as water diffusion showed a temperature effect with regard to the yield of gibberellin-like substances particularly during the first 6 h of diffusion. The yield of these substances is lower at 10°C, and remains lower as shown with consecutive diffusions, in comparison with the yields at 20°C or 30°C.With both agar and water diffusion the sum of activities obtained with consecutive diffusions is always higher, often considerably higher, than equal periods of continuous diffusion which is probably due to inactivation and/or interference of inhibitory substances with the bioassay responses. Finally, water diffusates of both seeds and seedlings of the normal growing cv. Violet of Japanese morning glory contained considerably more gibberellin-like activities than those of the dwarf cv. Kidachi which indicated that normals synthesize more gibberellins than dwarfs.     

Development and characterization of edible chitosan/olive oil emulsion films

The properties of plasticized chitosan-olive oil emulsion films prepared with increasing oil concentrations were investigated. Emulsifying nature of chitosan was enough to stabilize olive oil droplets in the film forming emulsions; hence homogeneous, thin and translucent films were obtained in all cases. The homogeneity of the lipid globules distribution in the films was confirmed by contact angle measurements and optical microscopy. All the tensile properties (Young Modulus, strength and maximum elongation) increased with olive oil concentration and were explained considering the interactions developed between lipid and carbohydrate phases in addition to the lubricant characteristics of the oil. Moisture sorption, water vapor permeation through the films and effective diffusion coefficients decreased as oil concentration increases, as a result of the non-polar nature of the lipid. Total soluble matter measurements were used to confirm the development of strong associations between chitosan and olive oil.     

Temperature dependence of water self-diffusion through lipid bilayers assessed by NMR

The temperature dependence of the coefficient of water self-diffusion across plane-parallel multib-ilayers of dioleoylphosphatidylcholine oriented on a glass support was studied in the 20–60°C range by pulsed field gradient NMR. The coefficient for transbilayer diffusion of water proved almost four orders of magnitude smaller than for bulk water, and 10 times smaller than that for lateral diffusion of lipid under the same conditions. The temperature dependence obeyed the Arrhenius law with apparent activation energy of 41 kJ/mol, much higher than that for bulk water (18 kJ/mol). The experimental data were analyzed using the “dissolution-diffusion” model, by simulating water passage through membrane channels, and by examining water exchange in states with different modes of translational mobility, including pore channels and bilayer defects. Each approach could take into account the role of bilayer permeability and assess the apparent activation energy for water diffusion in the hydrophobic part of the bilayer, which proved close to the value for bulk water. Estimates were obtained for water diffusion coefficients in the system, coefficients of bilayer permeability for water, and the influence of bilayer defects on the lateral and transverse diffusion coefficients.     

Combined analysis of diffusion and relaxation behavior of water in apple parenchyma cells

With apple parenchymal cells as an example, we demonstrate the expedience of combined analysis of the relaxation and diffusion of water molecules in plant cells by NMR spectroscopy. At small diffusion times, our approach discerns three relaxation components pertaining to water in the vacuole, cytoplasm, and intercellular space. The corresponding self-diffusion coefficients are determined. At long diffusion times, it is possible to distinguish two components. For the slow-relaxing component (vacuolar water) we observe the mode of restricted diffusion. For the fast-relaxing components, the diffusion coefficient anomalously increases with time.     

The self-diffusion of water in Artemia cysts

The self-diffusion coefficient of water molecules has been measured by nuclear magnetic resonance in cysts of Artemia over a wide range of hydration. Compared to the value for bulk water, the diffusion coefficient is reduced by a factor of 7 at the highest hydration and by approximately 100 at the lowest hydration. The results are used to evaluate various models that have been proposed to account for the reduction of water self-diffusion coefficients in complex systems.     

Water Binding in Legume Seeds

The physical status of water in seeds has a pivotal role in determining the physiological reactions that can take place in the dry state. Using water sorption isotherms from cotyledon and axis tissue of five leguminous seeds, the strength of water binding and the numbers of binding sites have been estimated using van't Hoff analyses and the D'Arcy/Watt equation. These parameters of water sorption are calculated for each of the three regions of water binding and for a range of temperatures. Water sorption characteristics are reflective of the chemical composition of the biological materials as well as the temperature at which hydration takes place. Changes in the sorption characteristics with temperature and hydration level may suggest hydration-induced structural changes in cellular components.