Pulsed Gradient Spin-echo NMR Research Articles

Understanding the spatial distribution of coke deposition within bimodal micro-/mesoporous catalysts using a novel sorption method in combination with pulsed-gradient spin-echo NMR

A new method for the determination of the spatial distribution of metal surface area within bimodal micro-/mesoporous solids has been developed. This novel technique involves incorporating a nonane pre-adsorption stage between two successive chemisorption experiments. This method has been used to probe the distribution of platinum amongst the micropores and mesopores of a range of bi-functional PtH-MFI catalysts, each possessing differing surface acidities, which have been used for benzene alkylation with ethane. It has been found that the catalyst with the lowest Si/Al ratio, and thus highest number of acid sites, also possessed the largest metal surface area within its microporosity. This catalyst was also the one that deactivated most rapidly, with coke being deposited predominantly within the micropore network. This was attributed to the bi-functional mechanism for coke formation at higher temperatures. Pulsed-gradient spin-echo NMR has also been used to show that a combination of higher mesopore platinum concentration and higher mass transport rates facilitated greater coke deposition within the mesoporosity.

Genistein Binding Mode to Doubly Nicked Dumbbell DNA. Dynamic and Diffusion Ordered NMR Study

New genistein derivatives were synthesized, which are fairly well soluble in water, with respect to parent genistein, and thus facilitate study of the interaction with dumbbell DNA dodecamer, mimicking the biological target for topoisomerase II inhibitors. A pulsed field gradient spin echo NMR experiment was used to check the binding and to estimate the association constants and its pH dependence of genistein with dumbbell DNA. Experimental restraints based on nuclear Overhauser spectroscopy spectra were used to calculate the NMR structure in solution in case of 6,8-disubstituted genistein with dimethylaminomethyl groups and were used in molecular modeling calculations. The structure is dynamic, and 10 molecular dynamics runs yield a family of conformations that essentially differ in a depth of inclusion of genistein into a nick. The paper experimentally shows evidence for binding, intercalation in the nick is proposed as a mode of genistein binding, and a model of the event is provided.

Designed post-self-assembly structural and functional modifications of a truncated tetrahedron.

Post-self-assembly modifications of a discrete metal-organic supramolecular structure have been developed. Such modifications allow the properties of the self-assembled supramolecular species to be changed in a simple and efficient manner (>90% yield). Initiated by the application of chemical stimuli, the post-self-assembly modifications described herein result in three distinct changes to the supramolecular system: an individual building-block component change, an overall structural modification, and a functional evolution of a [6+4] metal-organic supramolecular structure. The three modifications have been carefully examined by a range of characterization methods, including NMR and UV-vis spectroscopy, electrospray ionization mass spectrometry, pulsed field gradient spin echo NMR measurements, electrochemical analysis, and computational simulations.

β-Hairpin Peptide That Targets Vascular Endothelial Growth Factor (VEGF) Receptors

VEGF receptors have been the target of intense research aimed to develop molecules able to inhibit or stimulate angiogenesis. Based on the x-ray structure of the complex placental growth factor-VEGF receptor 1(D2), we designed a VEGF receptor-binding peptide reproducing the placental growth factor β-hairpin region Gln(87)-Val(100) that is involved in receptor recognition. A conformational analysis showed that the designed peptide adopts the expected fold in pure water. Moreover, a combination of NMR interaction analysis and cell binding studies were used to demonstrate that the peptide targets VEGF receptors. The VEGF receptor 1(D2)-interacting residues were characterized at the molecular level, and they correspond to the residues recognizing the placental growth factor sequence Gln(87)-Val(100). Finally, the peptide biological activity was characterized in vitro and in vivo, and it showed a VEGF-like behavior. Indeed, the peptide activated VEGF-dependent intracellular pathways, induced endothelial cell proliferation and rescue from apoptosis, and promoted angiogenesis in vivo. This compound is one of the few peptides known with proangiogenic activity, which makes it a candidate for the development of a novel peptide-based drug for medical applications in therapeutic angiogenesis.

Convection Effects on PGSE-NMR Self-Diffusion Measurements at Low Temperature: Investigation into Sources of Induced Convective Flows

The effects of convection on the measurement of the diffusion coefficients of liquids by the pulsed gradient spin echo (PGSE) NMR method at low temperature are discussed. To examine the generation of convective flows, we used four different types of sample tubes in the diffusion measurements with temperature variation; a normal 5 mm NMR tube, a Shigemi tube, an ELISE type tube, and a capillary tube. Below room temperature, the calculated diffusion coefficients of chloroform in 5 mm o.d. type tubes increased with decreasing temperature, while those in the capillary tube decreased linearly. The convective flow was found to be significant even at low temperature and it seemed to be mainly induced by the transverse temperature gradient. It was also found that the capillary tube was most appropriate to measure the diffusion coefficients, since its small diameter is effective in suppressing the convective flows at both high and low temperatures.

Consistent diffusion coefficients of ferrocene in some non-aqueous solvents: electrochemical simultaneous determination together with electrode sizes and comparison to pulse-gradient spin-echo NMR results

Cyclic voltammetry data recorded at disk macro- (millimeter dimension) and microelectrodes (10 and 100 μm) at various scan rates are used to simultaneously determine the diffusion coefficient D of ferrocene (fc) and the electroactive surfaces A and/or radii r of the electrodes. A case study with three electrodes of different sizes in CH3CN- and propylene carbonate (PC)-based electrolytes shows the possibly large effect of incorrect D values. Diffusion coefficients of fc are determined for PC, CH3CN, CH2Cl2, DMF, and DMSO electrolytes and (except for PC) compared to those from pulse-gradient spin-echo nuclear magnetic resonance experiments in the presence of supporting electrolyte in the respective deuterated solvents. The dependence of D fc on solvent viscosity is shown to follow the Stokes–Einstein relation.

Conformational consequences of cooperative binding of a coiled-coil peptide motif to poly(N-(2-hydroxypropyl) methacrylamide) HPMA copolymers

Small-angle neutron scattering and pulsed-gradient spin-echo NMR have been used to examine the solution conformation of a series of water soluble poly( N-(2-hydroxypropyl) methacrylamide) P(HPMA) co-polymer drug delivery vehicles incorporating a coiled-coil peptide motif as a novel pH sensitive non-covalent linker. The conformation of the HPMA homopolymer is well-described by a Gaussian coil model and changing pH from pH 7 to pH 5 has little effect on the solution conformation, as quantified via the radius of gyration. Copolymerisation with 5–10 mol% of the K3 peptide bearing methacrylate monomer (K3-MA), gave a series of copolymers that exhibited an increase in radius of gyration at both pH's, despite being typically 30% lower in molecular weight, indicating that the K3-MA causes a perturbation (expansion) of the copolymer conformation. Subsequent addition of an equimolar amount of the complementary peptide E3 makes little further difference to the conformation, indicative of the intimate binding (coiled-coil motif) between the two peptides. Again, the effects of pH are small. Only the addition of a large aromatic structure such as methotrexate causes a further perturbation of the structure — the hydrophobic interaction between the MTX units causes a significant collapse of the polymer coil. These findings further elaborate the understanding of those factors that determine the solution conformation of novel polymer therapeutics.

Apparent exchange rate mapping with diffusion MRI

Water exchange through the cell membranes is an important feature of cells and tissues. The rate of exchange is determined by factors such as membrane lipid composition and organization, as well as the type and activity of aquaporins. A method for noninvasively estimating the rate of water exchange would be useful for characterizing pathological conditions, e.g., tumors, multiple sclerosis, and ischemic stroke, expected to be associated with a change of the membrane barrier properties. This study describes the filter exchange imaging method for determining the rate of water exchange between sites having different apparent diffusion coefficients. The method is based on the filter-exchange pulsed gradient spin-echo NMR spectroscopy experiment, which is here modified to be compatible with the constraints of clinical MR scanners. The data is analyzed using a model-free approach yielding maps of the apparent exchange rate, here being introduced in analogy with the concept of the apparent diffusion coefficient. Proof-of-principle experiments are performed on microimaging and whole-body clinical scanners using yeast suspension phantoms. The limitations and appropriate experimental conditions are examined. The results demonstrate that filter exchange imaging is a fast and reliable method for characterizing exchange, and that it has the potential to become a powerful diagnostic tool.

Diffusion and Interfacial Transport of Water in Nafion

Water absorption, membrane swelling, and self-diffusivity of water in 1100 equivalent weight Nafion were measured as functions of temperature and water activity. Free volume per water at 80 °C, determined from water uptake and volume expansion data, decreases with water content in the membrane from 12 cm(3)/mol at λ = 0.5 H(2)O/SO(3) to 1.5 cm(3)/mol at λ = 4. The change in free volume with water content displays a transition at λ = 4. Limiting water self-diffusivity in Nafion was determined by pulsed gradient spin echo NMR at long delay times. The limiting self-diffusivity increases exponentially with water activity; the rate of increase of diffusivity with water content shows a transition at λ = 4. The tortuosity of the hydrophilic domains in Nafion decreased from 20 at low membrane water activity to 3 at λ = 4. It suggested a change in the connectivity of the hydrophilic domains absorbed water occurs at λ ∼ 4. The diffusivity results were employed to separate the contributions of diffusional and interfacial resistance for water transport across Nafion membranes, which enabled the determination of the interfacial mass transport coefficients. A diffusion model was developed which incorporated activity-dependent diffusivity, volume expansion, and the interfacial resistance, and was used to resolve the water activity profiles in the membrane.

Homogeneous length scale of shear-induced multilamellar vesicles studied by diffusion NMR

A recently developed protocol for pulsed gradient spin echo (PGSE) NMR is applied for the size determination of multilamellar vesicles (MLVs). By monitoring the self-diffusion behavior of water, the technique yields an estimate of the homogeneous length scale λ hom, i.e. the maximum length scale at which there is local structural heterogeneity in a globally homogeneous material. A cross-over between local non-Gaussian to global Gaussian diffusion is observed by varying the experimentally defined length- and time-scales. Occasional observation of a weak Bragg peak in the PGSE signal attenuation curves permits the direct estimation of the MLV radius in favorable cases, thus yielding the constant of proportionality between λ hom and radius. The microstructural origin of the Bragg peak is verified through Brownian dynamics simulations and a theoretical analysis based on the center-of-mass diffusion propagator. λ hom is decreasing with increasing shear rate in agreement with theoretical expectations and results from 2H NMR lineshape analysis.

Electrochemical studies and self diffusion coefficients in cyclic ammonium based ionic liquids with allyl substituents

Several cyclic ammonium-based ionic liquids (ILs) with allyl substituent are synthesized, these allyl substituent ILs have high ionic conductivity (up to 4.72 mS cm −1 at 30 °C) and wide electrochemical window of 5 V. The electrochemical behaviors of two organometallic redox couples Fc/Fc + (ferrocene/ferrocenium) and Cc/Cc + (cobaltocene/cobaltocenium) have been studied in these ILs, the calculated Stokes–Einstein product ( Dη T −1) of ferrocene in ILs is larger than that of cobaltocenium in ILs. The self-diffusion coefficients of cation and anion in these ILs are studied using pulsed gradient spin-echo NMR technique. There are very few reports where electrochemically derived diffusion coefficients and self diffusion coefficients are available for comparison, so a new key concept in electrochemistry could be developed in this paper.

Temperature and Hydration-Dependent Rotational and Translational Dynamics of a Polyether Oligomer

Temperature-dependent rotational diffusion of tetraethylene glycol dimethyl ether (TEGDE) is measured by optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy and compared to previous measurements of rotational diffusion as a function of water content. Both types of data, temperature-dependent and hydration-dependent, follow the Debye-Stokes-Einstein (DSE) equation and agree quantitatively with hydrodynamic calculations. Of particular importance is the result that both types of data show nearly identical dependence on the viscosity divided by the temperature (η/T). We also compare the translational diffusion constants as previously measured by pulsed field gradient spin-echo (PFG-SE) NMR as a function of both temperature and water content. The temperature-dependent data follow the Stokes-Einstein (SE) equation. Similar to the rotation, the low water content mixtures obey the SE equation and show the same proportionality to η/T as the temperature-dependent data. At higher water fractions, the data do not obey the SE equation. The principal results are that the influence of temperature on dry TEGDE orientational relaxation is the same as the influence of water content at fixed temperature, and that the influence of temperature on translational diffusion of dry TEGDE is the same as the influence of water content over a range of relatively low water concentrations. The results demonstrate that there are no large TEGDE structural changes or specific, long-lived water-polyether interactions in the solutions over the entire concentration range.

Responsive hybrid block co-polymer conjugates of proteins–controlled architecture to modulate substrate specificity and solution behaviour

Responsive co-polymers based on polyethyleneglycol methacrylate (PEGMA) monomers have been grown by aqueous phase ATRP from a model protein, trypsin, to generate hybrid polymer-protein block conjugates. The conjugates (Hybrids I and II) both contained the same segment of grafted responsive co-polymer to afford a phase transition at 37 °C, Hybrid II however differed from Hybrid I by having a second block of hydrophilic pPEGMA monomer grown from the end of the responsive block. The resultant ‘diblock’ and ‘triblock’ hybrids were characterised in terms of their temperature-dependent behaviour in solution by dynamic light scattering, small-angle neutron scattering and pulsed-gradient spin-echo NMR, and their structures at surfaces examined by aqueous phase atomic force microscopy and cryo transmission electron microscopy. These data showed that Hybrids I and II differed in their solution behaviour with temperature, dependent on the arrangement of their grafted polymer blocks. Hybrid I self-assembled into higher-order structures above 37 °C before precipitating reversibly, whereas Hybrid II remained essentially constant in size across a similar temperature range even when its attached intermediate polymer block underwent a phase transition. The differences in polymer-protein hybrid behaviour were also manifest in enzyme activity assays with temperature-dependent hydrolysis of both peptide and protein substrates varying with hybrid architecture. Overall the data show that it is possible to grow responsive polymer-protein block co-polymers of varied structures, architectures and solution behaviour and that these can be used to control bioconjugate activity.

Chemiluminescence of phthalhydrazide derivatives in organized media: Interactions with surfactants and cyclodextrins

The chemiluminescent oxidation of some phthalhydrazide derivatives, luminol (LUM), isoluminol (ISOL), N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and N-(6-aminohexyl)-N-ethylisoluminol (AHEI), has been carried out in micellar media and in the presence of natural cyclodextrins (CDs), using Co(II) as catalyst and H2O2 as oxidant. The cationic cetyltrimethylammonium bromide (CTAB) and, in a lesser extent, the anionic sodium dodecyl sulfate (SDS) produce quenching in the chemiluminescence (CL) of all the luminophores at concentrations above the cmc, whereas slight enhancements are attained with the non-ionic pentaethylene glycol monododecyl ether (C12E5). On the contrary, the incorporation of the CDs to the reaction produces a remarkable intensification of the CL. Binding of the luminophores to the macrocycles and the micelles has been studied by Pulsed-Gradient-Spin-Echo-NMR (PGSE-NMR) and fluorescence anisotropy. The cationic CTAB decreases the emission mainly due to charge compensation as a result of the association of the luminophores and the luminescent intermediates to the micelles. The presence of the alkyl substituents of ABEI and AHEI provides an additional hydrophobic contribution to the binding process. SDS quenches this reaction as the micelles retain Co(II) on their anionic layer. The protection and stabilization of these luminophores or their luminescent intermediates provided by the cavities of the CDs make this family of cyclic oligosaccharides much more suitable agents than the surfactants for enhancing the CL in aqueous media for this specific reaction.

Proton Transport Properties in Zwitterion Blends with Brønsted Acids

We describe zwitterion, 3-(1-butyl-1H-imidazol-3-ium-3-yl)propane-1-sulfonate (Bimps), mixtures with 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfoneamide (HN(Tf)(2)) as new proton transport electrolytes. We report proton transport mechanisms in the mixtures based on results from several methods including thermal analyses, the complex-impedance method, and the pulsed field gradient spin echo NMR (pfg-NMR) method. The glass transition temperature (Tg) of the mixtures decreased with increasing HN(Tf)(2) concentration up to 50 mol %. The Tg remained constant at -55 °C with further acid doping. The ionic conductivity of HN(Tf)(2) mixtures increased with the HN(Tf)(2) content up to 50 mol %. Beyond that ratio, the mixtures showed no increase in ionic conductivity (10(-4) S cm(-1) at room temperature). This tendency agrees well with that of Tg. However, the self-diffusion coefficients obtained from the pfg-NMR method increased with HN(Tf)(2) content even above 50 mol % for all component ions. At HN(Tf)(2) 50 mol %, the proton diffusion of HN(Tf)(2) was the fastest in the mixture. These results suggest that Bimps cannot dissociate excess HN(Tf)(2), that is, the excess HN(Tf)(2) exists as molecular HN(Tf)(2) in the mixtures. The zwitterion, Bimps, forms a 1:1 complex with HN(Tf)(2) and the proton transport property in this mixture is superior to those of other mixing ratios. Furthermore, CH(3)SO(3)H and CF(3)SO(3)H were mixed with Bimps for comparison. Both systems showed a similar tendency, which differed from that of the HN(Tf)(2) system. The Tg decreased linearly with increasing acid content for every mixing ratio, while the ionic conductivity increased linearly. Proton transport properties in zwitterion/acid mixtures were strongly affected by the acid species added.

Mechanistic Study of the Stereoselective Polymerization of d,l-Lactide Using Indium(III) Halides

We report the results of a comprehensive investigation of the recently discovered stereoselective and controlled polymerization of racemic lactide (D,L-LA) using an initiator prepared in situ from indium(III) chloride (InCl(3)), benzyl alcohol (BnOH), and triethylamine (NEt(3)). Linear relationships between number-average molecular weight (M(n)) and both monomer to alcohol concentration ratio and monomer conversion are consistent with a well-controlled polymerization. Studies on polymerization kinetics show the process to be first-order in [InCl(3)](0) and zero-order in both [BnOH](0) and [NEt(3)](0). The rate of D,L-LA conversion is also dependent on the indium(III) halide (i.e., t(1/2)(InCl(3)) approximately = 43 min versus t(1/2)(InBr(3)) approximately = 7.5 h, 21 degrees C, CD(2)Cl(2), [D,L-LA](0)/[BnOH](0) approximately = 100, [D,L-LA](0) = 0.84 M, [InX(3)](0)/[BnOH](0) = 1) and lactide stereoisomer (i.e., k(obs)(D,L-LA) approximately = k(obs)(meso-LA) > k(obs)(L-LA)). A model system that polymerizes D,L-LA with the same high degree of stereoselectivity was developed using 3-diethylamino-1-propanol (deapH) in lieu of BnOH and NEt(3). The product of the reaction of deapH with InCl(3) was identified as [InCl(3)(deapH)(H(2)O)](2) by elemental analysis, X-ray crystallography, and NMR and FTIR spectroscopies. An anhydrous version of the complex was also isolated when care was taken to avoid adventitious water, and was shown by pulsed gradient spin-echo (PGSE) NMR experiments to adopt a dinuclear structure in CD(2)Cl(2) solution under conditions identical to those used in its stereoselective polymerization of D,L-LA. The combined data suggest that the initiating species for the InCl(3)/BnOH/NEt(3) system is similar to [InCl(3)(deapH)(H(2)O)](2) and of the type [InCl((3-n))(OBn)(n)](m). With this information we propose a mechanism that rationalizes the observed stereocontrol in D,L-LA polymerizations. Finally, in an exploration of the scope of the InCl(3)/BnOH/NEt(3) system, we found this system to be effective for the polymerization of other cyclic esters, including epsilon-caprolactone and several substituted derivatives.

On the equality of interfacial and critical composition

It is shown that interfacial composition of the liquid–liquid interfaces is equal to the critical composition. The idea has been rigorously proven for binary regular solutions and has been reasonably supported for non-regular multicomponents, making use of the experimental mutual solubility data and the available information on titration, pulsed gradient spin-echo NMR, and differential scanning calorimetry of some W/O and O/W microemulsions. Using this finding, we, moreover, developed a simple equation for prediction of plait point concentration, having known just one tie-line data. The equation suggests a simple consistency test for measured solubility data, which is shown reliable for a large number of ternary systems. A molecular dynamic simulation also has been performed to support the idea.

Morphological and physiological modifications of cyanobacteria in experimental cyanobacterium-actinomycete associations

Associations of cyanobacteria and actinomycetes were formed experimentally from the cyanobacterium Anabaena variabilis ATCC 29413 and the streptomycetes isolated from apogeotropic roots of sago plants. Based on their phenotypic properties and the 16S rRNA gene sequencing, the streptomycetes were identified as representatives of Streptomyces pluricolorescens (strains 1 and 2). Cyanobacteria developing in monoculture and in association with an actinomycete were essentially different in their morphological and physiological-biochemical characteristics. In associations, cyanobacteria showed a higher (by tens of times) nitrogen-fixing activity compared to the monoculture and the morphological modifications of which were not observed in the monoculture (increase in cell size, increase in the portion of heterocysts among vegetative cells, appearance of the forms of unbalanced growth of cyanobacteria as giant, disc-shaped, curved, and rhomboid cells). At extremely low humidity (aw 0.50), associated cyanobacterial cells remained viable, whereas in the monoculture, chlorophyll decomposition and cells death occurred. The methods of high-resolution (H1 600 MHz) nuclear magnetic resonance (NMR) and pulsed-gradient spin echo NMR revealed a fraction of mobile protons in lyophilized samples of the cyanobacterium-actinomycete association, which was evidence of the presence of free water. This fraction was not found in the lyophilized samples of cyanobacterial and streptomycete monocultures. The revealed differences can explain the survival of cyanobacterial cells in associations.

Spectroscopic and Computational Insight into the Intermolecular Interactions between Zwitter‐Type Ionic Liquids and Water Molecules

Geometric and conformational changes of zwitter-type ionic liquids (ZILs) due to hydrogen-bonding interactions with water molecules are investigated by density functional theory (DFT), two-dimensional IR correlation spectroscopy (2D IR COS), and pulsed-gradient spin-echo NMR (PGSE NMR). Simulation results indicate that molecular structures in the optimized states are strongly influenced by hydrogen bonding of water molecules with the sulfonate group or imidazolium and pyrrolidinium rings of 3-(1-methyl-3-imidazolio)propanesulfonate (1) and 3-(1-methyl-1-pyrrolidinio)propanesulfonate (2), respectively. Concentration-dependent 2D IR COS reveals kinetic conformational changes of the two ZIL-H(2)O systems attributable to intermolecular interactions, as well as the interactions of sulfonate groups and imidazolium or pyrrolidinium rings with water molecules. The dramatic changes in the (1)H self-diffusion coefficients elucidate the formation of proton-conduction pathways consisting of ZIL networks. In ZIL domains, protons are transferred by a Grotthuss-type mechanism through formation, breaking, and restructuring of bonds between ZILs and H(2)O, leading to an energetically favorable state. The simulation and experimental investigations delineated herein provide a perspective to understanding the interactions with water from an academic point of view as well as to designing ILs with desired properties from the viewpoint of applications.

Hydrodynamic size and scaling relations for linear and 4 arm star PVAc studied using PGSE NMR

In this work the hydrodynamic radius and scaling relations of linear and 4 arm polyvinyl acetate (PVAc) were calculated from self-diffusion measurements. Self-diffusion coefficients at infinite dilution were estimated from measurements of self-diffusion at 25 °C in deuterated chloroform and in the dilute regime using pulsed gradient spin-echo (PGSE) nuclear magnetic resonance (NMR). Scaling laws were observed but unexpectedly these star polymers showed slightly larger hydrodynamic radii than the linear equivalents. Hydrodynamic radii were calculated for different Perrin or shape factors (i.e. spherical, cylindrical and ellipsoidal), and the equivalent hydrodynamic radii for the cylinders and ellipsoids were compared to those obtained for a spherical shaped molecule. These were also compared to an approximate equivalent hydrodynamic radius estimated using approximate dimensions of the polymers at maximum extension for the cylinder/ellipsoid molecular shapes. Results for cylinder and ellipsoid shapes were almost identical for the same aspect ratios as expected.