Pulsed Gradient Spin-echo NMR Research Articles

A theoretical study of the biselective double pulsed field gradient spin-echo NMR experiment

The application of a biselective radiofrequency pulse to a coupled homonuclear spin system produces effects that are exploited in liquid-state NMR experiments. The insertion of such an RF pulse in a double pulsed field gradient spin echo sequence results in a module for the biselective production of antiphase magnetization states. Biselectivity is obtained through cosine modulation of a singly selective pulse profile. A full description of the module behaviour is possible by means of four parameters, of which two are related to a property called ‘pulse ellipticity’. The theory is in good agreement with the experimental results and numerical simulations. It is thus possible to predict how a maximum of antiphase magnetization can be produced.

Self-Assembly and Encoding of Polymer-Stabilized Gold Nanoparticles with Surface-Enhanced Raman Reporter Molecules

Polymer-stabilized gold nanoparticles (AuNPs) were prepared and encoded with a range of surface-enhanced Raman reporter molecules. A range of as-synthesized polymers produced by reversible addition fragmentation chain transfer (RAFT) polymerization were demonstrated to self-assemble at the surface of AuNPs dispersed in water. The method involved the coprecipitation of polymer-gold conjugates by the addition of polymer dissolved in a water-miscible solvent to gold AuNPs dispersed in water. This method represents a simplification of the preparation of polymer-stabilized AuNPs compared with other published methods, in that the AuNPs do not need to be first transferred to an organic solvent. The process enabled the polymer stabilized AuNPs to be easily recovered by filtration or by phase transfer of the AuNPs to an organic solvent in which the RAFT polymer was soluble. The polymer-stabilized AuNPs were characterized by a range of methods including UV-visible spectrophotometry, transmission electron microscopy, thermogravimetric analysis, dynamic light scattering, and attenuated total reflection Fourier transform infrared spectroscopy. Furthermore, 1H pulsed field gradient spin echo NMR was utilized to characterize the self-diffusion of the polymer-stabilized AuNPs. Finally, we then demonstrated that these polymer-stabilized AuNPs maintained their ability to be encoded with surface-enhanced Raman spectroscopy reporter molecules.

Micelle–Vesicle Transition of Fatty Acid Based Ion‐Pair Surfactants: Interfacial Evidence and Influence of the Ammonium Counterion Structure

We describe the synthesis and the physicochemical study of new ion-pair amphiphiles from a mixture of bicyclic, cyclic, linear or branched amines and fatty acids of three chain lengths. Surface-tension measurements of bicyclic, cyclic and branched structures of ammonium/alkanoate acid ion pairs show a phase transition, with two plateaux in the plot of surface tension versus log(c) (c=concentration). Such behaviour is related to the structure of the counterion, the alkyl chain length and the temperature. Pulsed gradient spin echo NMR spectroscopy experiments were performed to demonstrate the existence of micelles on the first plateau and to confirm the phase transition. The existence of vesicles on the second plateau of the surface tension was proved by CryoTEM observation and dynamic light scattering (DLS) measurements. Mainly, according to the structure of the counterion, there is either a strong association and a positioning along the chain leading to vesicles or a less strong association leading to external positioning and the formation of micelles at low concentrations or vesicles at higher concentrations.

Preparation and Solution Behavior of a Thermoresponsive Diblock Copolymer of Poly(ethyl glycidyl ether) and Poly(ethylene oxide)

A thermoresponsive diblock copolymer, poly(ethyl glycidyl ether)-block-poly(ethylene oxide) (PEGE-b-PEO), is synthesized by successive anionic ring-opening polymerization of ethyl glycidyl ether and ethylene oxide using 2-phenoxyethanol as a starting material, and its solution behavior is elucidated in water. In a dilute 1 wt % solution, the temperature-dependent alteration in the polymer hydrodynamic radius (RH) is measured in the temperature range between 5 and 45 degrees C by pulse-gradient spin-echo NMR and dynamic light scattering. The RH value increased with temperature in two steps, where the first step at 15 degrees C corresponds to the core-shell micelle formation and the second step at 40 degrees C corresponds to the aggregation of the core-shell micelles. The formation of the core-shell micelles is supported by the solubilization of a dye (1,6-diphenyl-1,3,5-hexatriene) in the hydrophobic core, which is recognized for a copolymer solution in the temperature range between 20 and 40 degrees C. In this temperature range, the core-shell micelles and the unimers coexist and the fraction of the former gradually increases with increasing temperature, suggesting equilibrium between the micelles and the unimers. In the concentrated regime (40 wt % solution), the solution forms a gel and the small-angle X-ray scattering measurements reveal the successive formation of hexagonal and lamellar liquid crystal phases with increasing temperature.

Method for modeling transport of particles in realistic porous networks: Application to the computation of NMR flow propagators

We model the transport of particles present in a fluid steadily flowing through a porous medium. The porous medium is described by a representative three-dimensional network. The particles are subjected to advection by the flow and to thermal diffusion. We propose to calculate their trajectories with the continuous time random walk framework. This enables us to efficiently sample disordered networks with realistic topology. The method proposed in this paper is general and can be adapted to model dispersion of tracers. It is applied here to simulate the measurement of the flow propagator [Formula: see text] which is defined as the ensemble density distribution of tracer displacements [Formula: see text], in a given time interval delta t. It can be extracted from pulsed magnetic field gradient spin echo NMR experiments carried out on porous media while fluid is flowing. Preliminary numerical results show good qualitative agreement with experiments.

Derivatizing weak polyelectrolytes—Solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine)

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

Structure of SDS Micelles with Propylene Carbonate as Cosolvent: a PGSE−NMR and SAXS Study

The effect of propylene carbonate on SDS micelles was investigated by means of pulsed gradient spin-echo (PGSE) NMR, small-angle X-ray scattering (SAXS), conductivity and ion-selective electrode (ISE) measurements. The knowledge of the cosolvent partition between continuous phase and micelles (obtained by means of PGSE-NMR) allowed the identification of relevant dilution paths. Along these paths the system is composed of identical micelles that become more and more diluted. The extrapolation of measured self-diffusion coefficient to infinite dilution (where direct and hydrodynamic interactions are negligible) permits the determination of hydrodynamic size of the micelles. Moreover, the micelle ionization degree (measured by means of ISE) combined with PGSE-NMR and conductivity data furnishes an estimate of the aggregation number without any assumptions on micellar shape. On the other hand, troublesome hydrodynamic interactions are irrelevant to SAXS, and scattering data collected at fixed composition can be analyzed according to a reasonable model by exploiting the insight on the propylene carbonate partition gained through PGSE-NMR. By means of these approaches, we have found that propylene carbonate acts mainly as cosurfactant for the SDS micelles, decreasing their size and aggregation number by increasing the mean headgroup area of SDS.

Interaction between pentaethylene glycol n-octyl ether and poly(acrylic acid): Effect of the polymer molecular weight

The effect of the polymer molecular weight on the interaction between pentaethylene glycol n-octyl ether (C 8E 5) and poly(acrylic acid) (PAA) has been investigated by a combined experimental strategy including tensiometry, potentiometry, calorimetry, fluorescence quenching and intradiffusion (pulsed gradient spin echo-NMR) measurements. PAA samples with an average molecular weight varying in a wide range ( M ¯ w = 2000 , 100,000, 250,000, and 450,000) have been considered. The measurements have been performed at constant polymer concentration (0.1% w/w) with varying surfactant molality. In all the considered systems, at low surfactant concentration, adsorption of surfactant monomers onto the polymer chain has been detected. At a C 8E 5 molality ( T 1 ) independent of the PAA M ¯ w , surfactant molecules start to aggregate, forming clusters to which the polymer co-participates. Above this concentration, the behavior of the system depends on M ¯ w . In fact, if polymer samples with high molecular weight ( M ¯ w ⩾ 100 , 000 ) are employed, all the added surfactant aggregates onto the polymer leading to the polymer saturation and, subsequently, to free micelles formation. Both saturation and free micellization occur at surfactant concentrations which are independent of the polymer molecular weight. C 8E 5 aqueous mixtures containing PAA with low molecular weight ( M ¯ w = 2000 ) behaves differently, in that, above T 1 , only a fraction ( ∼ 20 % ) of the added surfactant molecules interact with the polymer, forming aggregates to which more than one PAA chain participate. In this case, C 8E 5 free micellization occurs before polymer saturation. The experimental evidences have been interpreted in terms of the subtle balance between the various molecular interactions driving the surfactant–polymer aggregation.

Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies

This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted pi-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89 degrees) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant mubeta as high as -488,000 x 10(-48) esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r(33)) of approximately 330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics.

Removal of chromate from water by a new CTAB–silica gelatin composite

A novel composite able to remove hexavalent chromium Cr(VI) from aqueous solutions was obtained by adding the silica precursor tetraethoxysilane (TEOS) to the hexadecyltrimethylammonium bromide (CTAB) microemulsion-based gel. A physical characterization of the new matrix revealed high stability of the silica gelatin composite in water at high temperatures and at neutral pH. Good efficiency in removing chromate from neutral solutions was also demonstrated by the adsorption kinetics. In particular, the adsorption data of chromate obtained with the CTAB–silica gelatin composite at 25 °C and pH 7.5 are described by the Freundlich isotherm model. The specific role of CTAB in the silica gelatin composite was also evaluated by comparing the kinetics of the anionic AOT–silica gelatin composite to the CTAB one. The data collected clearly showed that the positively charged surfactant was necessary to efficiently adsorb Cr(VI) from aqueous solutions. SEM and pulsed gradient spin–echo NMR analysis of the composite demonstrated that the silicon is well assembled in the gelatin network, in which water molecules maintain a high mobility. The diffusion coefficient of water in this system was shown to remain close to the value of pure water. Finally, X-ray analyses of the elemental content in the CTAB–silica gelatin composite indicated no difference in terms of percentage of silica distributions in different areas of the matrix and suggested that chromium adsorption could take place in internal areas.

NMR Studies of Aggregation and Hydration of Surfactants Containing Amide Bonds

The consequences of including amide bonds into the structure of short-chain nonionic surfactants have been studied. Of particular interest were the possible effects of the hydrogen bonding ability of the amide group on the micellar shape. The aggregate structure and hydration of two different amide-containing surfactants, C7H15CO-NH-(CH2CH2O)4H and C7H15CO-(NH-C3H6-CO)2N(CH3)2, were investigated using NMR diffusometry (pulsed gradient spin echo NMR) as the main technique. Data from experiments on the surfactants, the hydrophobic probe molecule hexamethyldisilane (HMDS), and water were interpreted to gain information about the solution structures, and the results were compared to those on a previously studied alcohol ethoxylate surfactant of similar size, C8E4. Both of the amide-containing surfactants form small micelles within the whole investigated concentration range. At the critical micelle concentration, the aggregates are most probably spherical, and with increasing surfactant concentration there are indications of either a minor aggregate growth or agglomeration of the micelles. In addition, it was found that the presence of amide groups in the surfactant inhibits the intermicellar transport of HMDS, which occurs in the C8E4 system. From measurements on water diffusion in the three surfactant systems, it could be concluded that the surfactant hydration is higher when amide bonds are present.

A PGSE diffusion and electrophoretic NMR study of Cs+ and Na+ dynamics in aqueous crown ether systems

Multinuclear pulsed gradient spin-echo (PGSE) NMR diffusion and linewidth measurements were used to probe binding and transport in aqueous Na+-15-crown-5, Na+-18-crown-6, Cs+-15-crown-5 and Cs+-18-crown-6 systems. Since direct PGSE observation of many alkali cations is precluded by either low inherent sensitivity or rapid relaxation (or both), the feasibility of proton-detected electrophoretic NMR (ENMR) measurements to complement PGSE data was investigated. ENMR measurements were performed on aqueous Cs+-, Li+-, Na+-, K+-, and Rb+- 18-crown-6 systems. The data analysis is based on a two-site binding model and its corresponding association constants. Cs+ was found to bind considerably more tightly to 18-crown-6 (K=8 M-1) than to 15-crown-5 (K approximately 2 M-1), whereas Na+ had almost equal affinity (K approximately 4.5 M-1) for 15-crown-5 and 18-crown-6. The difficulties encountered in analysing the NMR parameters, methodological limitations and the implied need for more complicated binding models are discussed.

Direct in Situ Observation of Dynamic Transport for Electrolyte Components by NMR Combined with Electrochemical Measurements

Electrochemical studies provide broad, but not cation- or anion-specific information on the migration of charged ions. However, individual ion diffusion (as a weighted average of charged and neutral ions) can be measured using pulsed-gradient spin-echo (PGSE) NMR. In this paper, the lithium transport in an electrolyte including a lithium salt was measured using electrophoretic NMR (ENMR) with non-blocking electrodes. A propylene carbonate (PC) solution doped with LiN(SO(2)CF(3))(2) (LiTFSI) was inserted in a homemade NMR cell equipped with Li/Li electrodes. The drift migrations of lithium cation ((7)Li), anion ((19)F), and solvent ((1)H) were measured independently under potentials of up to 3.0 V. Greatly enhanced dynamic lithium transport was observed for the first time in the bulk electrolyte under an electric field closely related to real conditions in a rechargeable lithium battery.

Toolbox for 3D imaging and modeling of porous media: Relationship with transport properties

Porous media can be considered as interfacial systems where an internal surface partitions and fills the space in a complex way. Meaningful structural features appear on a length-scale where physical chemistry plays a central role either to impose a specific organisation on the material or to strongly modify the dynamics and the thermodynamics of the embedded fluids. A key issue is to understand how the geometrical and interfacial confinement affects numerous phenomena such as molecular diffusion, excitation relaxation, reaction kinetics, phase transitions, adsorption and capillary condensation. We will first review some experimental techniques able to image the 3D structure of disordered porous media. In the second part, we will analyse the geometrical and particularly some topological properties of a disordered porous material. We will discuss the interest and the limits of several strategies for obtaining 3D representations of various pore networks starting from an incomplete set of morphological characterisations. Finally, connection between geometry and diffusive transport will be presented, with emphasis on the application of pulsed gradient spin echo NMR technique as a tool for a multiscale analysis of transport in a confining geometry.

The effect of riboflavin-photoinduced degradation of alginate matrices on the diffusion of poly(oxyethylene) probes in the polymer network

The effect of irradiation, in the wavelength range of 310–800 nm, on the tracer diffusion of poly(oxyethylene) (POE) of different molecular weights embedded in various alginate matrices with the photosensitizer riboflavin (RF) present, has been investigated with the aid of pulsed field gradient spin-echo NMR (PGSE-NMR). Both alginate solutions of different polymer concentration were studied as well as corresponding acid gels of alginate produced by introduction of different amount of glucono-δ-lactone (GDL). In 2 wt.% alginate solutions, the values of the tracer diffusion coefficient suggest a strong obstruction effect as the probe molecular weight increases. Faster probe diffusion was observed for the irradiated samples, which indicates a photochemical scission of the polymer chains and the formation of a fragmented polymer network that facilitates the migration of the tracer chains. A semidilute alginate/RF solution was transformed into a gel by adding sufficient amount of GDL. GDL lowers the pH of the solution under the pK a of alginate, favouring intermolecular associations and the evolution of a less homogeneous network with more open structure. Therefore, the POE chains were shown to diffuse faster in the acid gel matrix than in the corresponding more homogeneous alginate solutions. The photochemically induced cleavage again promoted faster migration of the probe chains in the irradiated samples. The probe diffusion of the eight-arm star-shaped POE sample revealed an augmented obstruction effect with increasing alginate concentration and higher values of the diffusion coefficient were found in gels. The evolution of a tighter network inhibits the diffusion of the probe molecules. At lower alginate concentrations the values of the tracer diffusion coefficients are higher for the irradiated samples than for the non-exposed systems.

A comparative study of the properties of polar and nonpolar solvent/solute/polystyrene solutions in microwave fields via molecular dynamics

The influence of an applied microwave field on the dynamics of methylamine-dichloromethane (DCM) mixtures bound within atactic polystyrene (a-PS) over a range of polymer densities from 30 to 94 wt % polymer was examined using atomistic molecular dynamics simulations. This study is an extension of previous studies on methylamine transport in relatively polar polystyrene solutions of methanol and dimethylformamide [M. J. Purdue et al., J. Chem. Phys. 124, 204904 (2006)]. A direct comparison is made across the three types of polystyrene solutions. Consideration is given to both solvent and reagent transport within the polymer solutions under zero-field conditions and in an external electromagnetic field in the canonical ensemble (NVT) at 298.0 K. Various frequencies up to 10(4) GHz and a rms electric field intensity of 0.1 VA were applied. The simulation studies were validated by comparison of the simulated zero-field self-diffusion coefficients of DCM in a-PS with those obtained using pulsed-gradient spin-echo NMR spectrometry. Athermal effects of microwave fields on solute transport behavior within polymer solutions are discussed.

7Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic–inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

Organic–inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO 4 via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10 −3 S/cm at 30 °C. Variable temperature 7Li–{ 1H} magic angle spinning (MAS) NMR demonstrated that the Li + cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the 7Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.

Characterization of Chloroaluminate Molten Salts by Pulsed-Gradient Spin-Echo NMR

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Accounting for Spin Relaxation in Quantitative Pulse Gradient Spin Echo NMR Mixture Analysis

Pulsed gradient spin-echo (PGSE) NMR is intrinsically nonquantitative. Because the experiment is echo-based, differences in the relaxation behavior of the nuclei among the components give rise to varied intensities and lead to nonquantitative spectra. A method is presented that restores resolved, quantitative spectra from mixtures by processing data from several PGSE NMR experiments with varied delay times. The approach incorporates a simple data acquisition scheme and leads to a computationally fast, linear least-squares analysis. It is anticipated the method will be of much interest for performing mixture analysis of polymer solutions and the characterization of surface-modified nanoparticulate dispersions.

New Class of Aggregates in Aqueous Solution: An NMR, Thermodynamic, and Dynamic Light Scattering Study

We investigated the aggregation properties of two classes of aromatic and hydrophobic compounds, namely chloroacetamides and ethyl 3-phenyl-2-nitropropionates, in moderately concentrated aqueous solution (millimolar range). The identification of all species present in solution under specific experimental conditions was performed by 1D and 2D NMR, pulsed gradient spin-echo NMR, and dynamic light scattering techniques. Some physical-chemical properties (viscosity, surface tension, and colligative properties) of the aqueous solutions were also determined. Both classes of compounds behave quite similarly: in solution, three distinct species, namely a monomeric species, small and mobile aggregates, and large and stiff aggregates, are observed. The results give insight into a new class of aggregates, held together by pi-pi interactions, which show an unusual associative behavior in water.