Synergistic Properties of Arabinogalactan (AG) and Hyaluronic Acid (HA) Sodium Salt Mixtures

The properties of mixtures of two polysaccharides, arabinogalactan (AG) and hyaluronic acid (HA), were investigated in solution by the measurement of diffusion coefficients D of water protons by DOSY (Diffusion Ordered SpectroscopY), by the determination of viscosity and by the investigation of the affinity of a small molecule molecular probe versus AG/HA mixtures in the presence of bovine submaxillary mucin (BSM) by ¹HNMR spectroscopy. Enhanced mucoadhesive properties, decreased mobility of water and decreased viscosity were observed at the increase of AG/HA ratio and of total concentration of AG. This unusual combination of properties can lead to more effective and long-lasting hydration of certain tissues (inflamed skin, dry eye corneal surface, etc.) and can be useful in the preparation of new formulations of cosmetics and of drug release systems, with the advantage of reducing the viscosity of the solutions.     

Fine-tuning of the diffusion dimension of –OH groups for high resolution DOSY NMR applications in crude enzymatic transformations and mixtures of organic compounds

A convenient DOSY methodology was developed that can be applied directly in crude reaction products or mixtures containing polyphenol organic compounds, for the rapid identification of their various components without any prior separation or isolation. The method is based on the resolution enhancement of the resonances of the –OH protons and the fine-tuning of their diffusion coefficients to the molecular diffusion coefficient; this can be achieved in DMSO-d₆ in combination with the addition of picric acid and the use of temperatures near the freezing point of the solution. This method, which does not modify the apparent molecular diffusion, allowed the recording of high resolution DOSY spectra, both in crude enzymatic reactions and mixtures of organic compounds based on the phenolic OH NMR spectral region which is much less crowded and, thus, much more informative compared to the aromatic region.     

Molecular dynamics simulation on influence of temperature effect on electro-coalescence behavior of nano-droplets

In electric dehydration of crude oil, the dewatering efficiency can be improved by raising emulsion temperature properly which reduces the viscosity of crude oil. However, it should be noticed that the emulsion temperature does not only affect the emulsion viscosity but also nano-droplets dynamics behavior which impacts the coalescence efficiency either. Therefore the influence of temperature effect on the electro-coalescence of nano-droplets is studied by a molecular dynamics method. The results show that the temperature presents an active or negative effect, depending on the competitive relation between electrostatic interaction and thermal motion. Two stages are distinguished according to the dominant mechanism. During stage I, governed by the electrostatic interaction, lower temperature promotes the polarization and leads to an acceleration of the droplets coalescence, but higher temperature restrains the coalescence process due to molecules thermal motion breaking the polarization process. During stage II, governed by the thermal motion, lower temperature improves the coalescence because of a diffusion effect, but higher temperature deteriorates electro-coalescence because of a violent molecular thermal motion. Additionally, hydrogen bond and radial distribution functions are obtained by statistics to describe droplets micromorphology, which explains the reason why the droplet forms longer chain structure at the critical electric field.     

Using perdeuterated surfactant micelles to resolve mixture components in diffusion‐ordered NMR spectroscopy

Diffusion‐ordered NMR spectroscopy resolves mixture components on the basis of differences in their respective diffusion coefficients or molecular sizes. However, when components have near‐identical diffusion coefficients, they are not resolved in the diffusion dimension of a diffusion‐ordered spectroscopy (DOSY) spectrum. Adding surfactant micelles to these mixtures has been shown to enhance resolution when the component molecules interact differentially with the micelles. This approach is similar to that used in electrokinetic chromatography (EKC) where modifiers like micelles or polymers are used to enhance the separation of mixture components. In this study, perdeuterated surfactants are added to analyte mixtures studied with the DOSY technique. Since no micelle resonances appear in the mixture spectra, the difficulty associated with performing biexponential analyses in spectral regions where analyte and surfactant resonances overlap is avoided. The approach is demonstrated using mixtures of peptides with near‐identical diffusion coefficients. Copyright © 2008 John Wiley & Sons, Ltd.     

Rapid analysis of lubricants by atmospheric solid analysis probe–ion mobility mass spectrometry

Formulated lubricants are complex mixtures composed of base oil(s) and additives with various functions (detergents, corrosion inhibiter, antioxidant, viscosity modifiers, etc.). Because of the aliphatic nature of base oil and the chemical diversity of additives, the characterization of lubricant is currently a long and complex process. The comprehensive analysis of lubricant samples involves several techniques such as nuclear magnetic resonance, mass spectrometry, chromatography and infrared spectroscopy. The coupling of atmospheric solid analysis probe (ASAP) with ion mobility‐mass spectrometry (IM‐MS) has been shown to be an efficient tool for the characterization of complex mixture containing vaporizable polar to non‐polar compounds. This approach affords the coupling of a direct ionization technique that does not require sample preparation, with a bi‐dimensional separation method with high peak capacity. In this work, we show that ASAP‐IM‐MS is a suitable method for rapid and direct characterization of lubricant samples. Indeed, base oil and additives yielded, by ASAP, ions series which could be separated by IM‐MS. Molecular additives such as Zn‐dithiocarbamate, phosphite, thiophosphate and Alkyl diphenylamine were ionized as molecular ions [M]^+? or protonated molecules [M + H]⁺, depending of their polarity. In some cases, fragment ions were observed, confirming the additive identification. In addition, high molecular weight polymeric additives such as poly(alkyl methacrylate) (PAM) were pyrolized in the ASAP source leading to characteristic fragment ions. ASAP‐IM‐MS is shown to be a powerful tool for studying complex mixtures, allowing the first comprehensive analysis of lubricants in just a few minutes. Copyright © 2014 John Wiley & Sons, Ltd.     

Studies on supramolecular gel formation using DOSY NMR

Herein, we present the results obtained from our studies on supramolecular self‐assembly and molecular mobility of low‐molecular‐weight gelators (LMWGs) in organic solvents using pulsed field gradient (PFG) diffusion ordered spectroscopy (DOSY) NMR. A series of concentration‐dependent DOSY NMR experiments were performed on selected LMWGs to determine the critical gelation concentration (CGC) as well as to understand the behaviour of the gelator molecules in the gel state. In addition, variable‐temperature DOSY NMR experiments were performed to determine the gel‐to‐sol transition. The PFG NMR experiments performed as a function of gradient strength were further analyzed using monoexponential DOSY processing, and the results were compared with the automated Bayesian DOSY transformation to obtain 2D plots. Our results provide useful information on the stepwise self‐assembly of small molecules leading to gelation. We believe that the results obtained from these experiments are applicable in determining the CGC and gel melting temperatures of supramolecular gels. Copyright © 2015 John Wiley & Sons, Ltd.     

Ionic diffusion and salt dissociation conditions of lithium liquid crystal electrolytes

Salt dissociation conditions and dynamic properties of ionic species in liquid crystal electrolytes of lithium were investigated by a combination of NMR spectra and diffusion coefficient estimations using the pulsed gradient spin-echo NMR techniques. Activation energies of diffusion (Ea) of ionic species changed with the phase transition of the electrolyte. That is, Ea of the nematic phase was lower than that of the isotropic phase. This indicates that the aligned liquid crystal molecules prepared efficient conduction pathways for migration of ionic species. The dissociation degree of the salt was lower compared with those of the conventional electrolyte solutions and polymer gel electrolytes. This is attributed to the low concentration of polar sites, which attract the dissolved salt and promote salt dissociation, on the liquid crystal molecules. Furthermore, motional restriction of the molecules due to high viscosity and molecular oriented configuration in the nematic phase caused inefficient attraction of the sites for the salt. With a decreased dissolved salt concentration of the liquid crystal electrolyte, salt dissociation proceeded, and two diffusion components attributed to the ion and ion pair were detected independently. This means that the exchange rate between the ion and the ion pair is fairly slow once the salt is dissociated in the liquid crystal electrolytes due to the low motility of the medium molecules that initiate salt dissociation.     

Synthesis and thermophysical properties of two new protic long-chain ionic liquids with the oleate anion

This work reports the synthesis of 2-hydroxy ethylammonium oleate and bis(2-hydroxy ethyl)ammonium oleate ionic liquids, which have a long aliphatic chain as well as the study of some of their physical properties, in particular the effect of temperature on their density, speed of sound, viscosity, and refractive index. ¹H and ¹³C NMR spectra were used to characterize the chemical structure of the species in concordance with FT-IR spectra. DOSY NMR spectra were used to determine the self-diffusion coefficients of 2-hydroxy ethylammonium oleate ionic liquid, which were consistent with the formation of a lamellar or micellar liquid crystal phase; due the similar structure, a similar aggregation in the bis(2-hydroxy ethyl)ammonium oleate ionic liquid it is expected.     

Diffusion measurements for molecular capsules: pulse sequences effect on water signal decay

Diffusion NMR and, more recently, diffusion ordered spectroscopy (DOSY) are gaining popularity as efficient tools for the characterization of supramolecular systems in solution. Here, using diffusion NMR of hydrogen-bond molecular capsules, we demonstrate that the use of different diffusion sequences may have a dramatic effect on exchanging peaks. In fact, we found that the signal decay of the water peak in [(1a)(6)(H(2)O)(8)] is monoexponential in the pulsed gradient spin-echo (PGSE) and stimulated echo (PGSTE) sequences and biexponential in the longitudinal eddy current delay (LED) and the bipolar longitudinal eddy current delay (BPLED) sequences, routinely used in modern DOSY experiments. By performing these diffusion measurements on molecular capsules, in which water is not part of the molecular capsules, we demonstrate that this phenomenon is observed only for water molecules that exchange between two sites that differ considerably in their diffusion coefficients. Degeneration of the LED or the BPLED sequences into PGSTE-type sequences by shortening the te period resulted in the disappearance of the extra slow diffusing component. The origin, as well as the implications of the different results obtained from conventional diffusion sequences, such as the PGSE and PGSTE as compared with the LED and BPLED sequences generally used in DOSY experiments, are briefly discussed.     

Pseudo-Restricted Self-Diffusion of Molecules in Biporous Structures: Study by Pulsed Field Gradient NMR

The mobility of liquid (n-decane) that fills the system of primary and secondary pores of a biporous sample (granular Vycor porous glass) is studied by the pulsed field gradient NMR technique. The anomalous time dependence of the slow component of diffusion decay is revealed: the self-diffusion coefficient decreases with an increase in diffusion time t_d and, at large t_d values, this dependence satisfies the feature of completely restricted self-diffusion. It is established that this component is related to the mobility of liquid molecules filling the system of primary pores. By use of computer simulation, it is shown that the effect of “pseudo-restricted” diffusion is explained by the exchange processes between the phases, where the molecules of the liquid that are present in the systems of primary and secondary pores and differ in self-diffusion coefficients are understood as the phases. The effect of interfacial exchange is confirmed by the time dependence of the fraction of molecules with the lowest self-diffusion coefficients. The revealed phenomenon of “pseudo-restricted” diffusion is not related to real spatial constraints and can be observed in any systems with two (or more) phases with different self-diffusion coefficients, provided that these “phases” are bulky and can be subjected to molecular exchange.     

Mechanisms of the Diffusion of Nonpolar Substances in a Hydrophilic Ionic Liquid

The structural-dynamic features of ionic liquid-nonpolar substance systems are studied by means of molecular dynamics using Frenkel’s fundamental theory of a liquid and the phonon theory of the thermodynamics of a liquid, in combination with the DL_POLY_4.05 software package. Argon, methane, and benzene molecules serve as the dissolved substances. Model concepts are proposed and analyzed to describe the diffusion of molecules of a dissolved substance in an ionic liquid. It is shown that an increase in the mass of the molecules of a dissolved nonpolar substance correlates with their mobility in a hydrophilic ionic liquid (IL). This determines the diffusion of the components of dmim⁺/Cl^? IL solutions and is responsible for the anomalous behavior of the solubility of nonpolar substances in them.     

Quantitative evaluation on oil diffusion mechanisms in nano‐organic‐montmorillonite modified caster oil‐based polyurethane foam for oil/water separation

To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10^?4 cm²/s, 2.6 × 10^?4 cm²/s, 3.0 × 10^?4 cm²/s, 3.2 × 10^?4 cm²/s, and 3.3 × 10^?4 cm²/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.     

Metal‐Directed Self‐Assembly of a Polyoxometalate‐Based Molecular Triangle: Using Powerful Analytical Tools to Probe the Chemical Structure of Complex Supramolecular Assemblies

A polyoxometalate‐based molecular triangle has been synthesized through the metal‐driven self‐assembly of covalent organic/inorganic hybrid oxo‐clusters with remote pyridyl binding sites. The new metallomacrocycle was unambiguously characterized by using a combination of ¹H NMR spectroscopy, 2D diffusion NMR spectroscopy (DOSY), electrospray ionization travelling wave ion mobility mass spectrometry (ESI‐TWIM‐MS), small‐angle X‐ray scattering (SAXS) and molecular modelling. The collision cross‐sections obtained from TWIM‐MS and the hydrodynamic radii derived from DOSY are in good agreement with the geometry‐optimized structures obtained by using theoretical calculations. Furthermore, SAXS was successfully employed and proved to be a powerful technique for characterizing such large supramolecular assemblies.     

Matrix-Assisted DOSY for Analysis of Indole Alkaloid Mixtures

Diffusion-ordered spectroscopy (DOSY) is a powerful tool for investigating mixtures and identifying peaks of chemical components. However, similar diffusion coefficients of the components, particularly for complex mixtures that contain crowded resonances, limit resolution and restrict application of the DOSY technique. In this paper, matrix-assisted DOSY were used to explore whether the diffusion resolution of a complex model involving indole alkaloid mixtures can be realized. Furthermore, we investigated the influence of different factors on the separation effect. The results showed that the changes in diffusion coefficient differences were achieved more obviously when using sodium dodecyl sulfate (SDS) micelles as the matrix. In addition, we also found that increasing the concentration of SDS can improve the resolution of the DOSY spectrum. Finally, after investigating the influence factors and NMR conditions, we demonstrated the applications of the SDS-assisted DOSY on analyzing the total alkaloid extract of Alstonia Mairei, and the virtual separation of mixtures was achieved.     

How does the mobility of phospholipid molecules at a water/oil interface reflect the viscosity of the surrounding oil?

The mobility of phospholipid molecules at a water/oil interface on cell-sized phospholipid-coated microdroplets was investigated through the measurement of diffusion constants by fluorescence recovery after photobleaching. It is found that the diffusion constant of phospholipids showed the relation D approximately (eta water + eta oil) -0.85, where D is the diffusion constant, eta water is the viscosity of water, and eta oil is the viscosity of oil. This observation indicates that the viscosity of the surrounding oil is the primary factor that determines the diffusibility of phospholipids at a water/oil interface.     

Use of glass capillaries to suppress thermal convection in NMR tubes in diffusion measurements

Diffusion ordered spectroscopy (DOSY) is used to determine the translational diffusion coefficients of molecules in solution. However, DOSY is highly susceptible to spurious spectral peaks resulting from thermal convection occurring in the NMR tube. Thermal convection therefore must be suppressed for accurate estimation of translational diffusion coefficients. In this study, we developed a new method to effectively suppress thermal convection using glass capillaries. A total of 6 to 18 capillaries (0.8‐mm outer diameter) were inserted into a regular 5‐mm NMR tube. The capillaries had minimal effect on magnetic field homogeneity and enabled us to obtain clean DOSY spectra of a mixture of small organic compounds. Moreover, the capillaries did not affect chemical shifts or signal intensities in two‐dimensional heteronuclear single quantum coherence spectra. Capillaries are a simple and inexpensive means of suppressing thermal convection and thus can be used in a wide variety of DOSY experiments. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of polymer architecture on self‐diffusion of LC polymers

Two LC side‐group poly(methacrylates) were synthesized, and their melt dynamics were compared with each other and a third, main‐chain side‐group combined LC polymer. A new route was developed for the synthesis of the poly(methacrylate) polymers which readily converts relatively inexpensive perdeuteromethyl methacrylate to other methacrylate monomers. Self‐diffusion data was obtained through the use of forward recoil spectrometry, while modulus and viscosity data were measured using rotational rheometers in oscillatory shear. Diffusion coefficients and complex viscosity were compared to previous experiments on liquid crystal polymers of similar architecture to determine the effect of side‐group interdigitation and chain packing on center of mass movement. The decyl terminated LC side‐group polymer possessed an interdigitated smectic phase and a sharp discontinuity in the self‐diffusion behavior at the clearing transition. In contrast, the self‐diffusion behavior of the methyl terminated LC side‐group polymer, which possessed head‐to‐head side‐group packing, was seemingly unaffected by the smectic–nematic and nematic–isotropic phase transitions. The self‐diffusion coefficients of both polymers were relatively insensitive to the apparent glass transition. The presence of moderately fast sub‐T_g chain motion was supported by rheological measurements that provided further evidence of considerable molecular motion below T_g. The complex phase behavior of the combined main‐chain side‐group polymer heavily influenced both the self‐diffusion and rheological behavior. Differences between the self‐diffusion and viscosity data of the main‐chain side‐group polymer could be interpreted in terms of the defect structure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 405–414, 1999     

Accurate molecular weight determination of small molecules via DOSY-NMR by using external calibration curves with normalized diffusion coefficients

Determination of the aggregation and solvation numbers of organometallic complexes in solution is an important task to increase insight in reaction mechanisms. Thus knowing which aggregates are formed during a reaction is of high interest to develop better selectivity and higher yields. Diffusion-ordered spectroscopy (DOSY), which separates NMR signals according to the diffusion coefficient, finds increasing use to identify species in solution. However, there still is no simple relationship between diffusion coefficient and molecular weight (MW). Some methods have been developed to estimate the MW but still with a significant error of ±30%. Here we describe a novel development of MW-determination by using an external calibration curve (ECC) approach with normalized diffusion coefficients. Taking the shape of the molecules into account enables accurate MW-predictions with a maximum error of smaller than ±9%. Moreover we show that the addition of multiple internal references is dispensable. One internal reference (that also can be the solvent) is sufficient. If the solvent signal is not accessible, 16 other internal standards (aliphatics and aromatics) are available to avoid signal overlapping problems and provide flexible choice of analytes. This method is independent of NMR-device properties and diversities in temperature or viscosity and offers an easy and robust method to determine accurate MWs in solution.     

Sterols associated with small unilamellar vesicles (SUVs): intrinsic mobility role for 1H NMR detection

Small unilamellar vesicles (SUVs) of phospholipids are often used as a membrane model system for studying the interaction of molecules. When using NMR under the standard liquid‐state conditions, SUV phospholipid proton spectra can be recorded, exhibiting sharp signals. This is not only because of the fast vesicular tumbling but also because of the combination of this tumbling with the individual motion of the lipids inside the bilayer. This appears evident because addition of cholesterol is responsible of broader resonances because of the slowing down of the lipid motion. On the other hand, no ¹H signal is detected for cholesterol in the bilayer. This lack of detection of the inserted molecules explains why generally SUVs are not considered as a good model for NMR studies under the standard liquid‐state conditions. Here, we use two other sterols in order to demonstrate that an increase of the molecular mobility inside the bilayer could allow the detection of their proton resonances. For desmosterol and lanosterol, which show higher mobility inside the bilayer, with increasing lateral diffusion rates, ¹H sterol signals are detected in contrast to cholesterol. For the fast diffusing lanosterol, no significant improvement in detection is observed using deuterated lipids, demonstrating that homonuclear dipolar coupling is fully averaged out. Furthermore, in the case of low mobility such as for cholesterol, the use of a fast magic angle spinning probe is shown to be efficient to recover the full proton spectrum. Copyright © 2014 John Wiley & Sons, Ltd.     

Molecular dynamics and composition of crude oil by low‐field nuclear magnetic resonance

Nuclear magnetic resonance (NMR) techniques are widely used to identify pure substances and probe protein dynamics. Oil is a complex mixture composed of hydrocarbons, which have a wide range of molecular size distribution. Previous work show that empirical correlations of relaxation times and diffusion coefficients were found for simple alkane mixtures, and also the shape of the relaxation and diffusion distribution functions are related to the composition of the fluids. The 2D NMR is a promising qualitative evaluation method for oil composition. But uncertainty in the interpretation of crude oil indicated further study was required. In this research, the effect of each composition on relaxation distribution functions is analyzed in detail. We also suggest a new method for prediction of the rotational correlation time distribution of crude oil molecules using low field NMR (LF‐NMR) relaxation time distributions. A set of down‐hole NMR fluid analysis system is independently designed and developed for fluid measurement. We illustrate this with relaxation–relaxation correlation experiments and rotational correlation time distributions on a series of hydrocarbon mixtures that employ our laboratory‐designed downhole NMR fluid analyzer. The LF‐NMR is a useful tool for detecting oil composition and monitoring oil property changes. Copyright © 2016 John Wiley & Sons, Ltd.