NMR study of the structure of poly(N-benzoyl-8-octanelactam)

The structure of a polymer prepared by the polymerization of N-benzoyl-8-octanelactam initiated with benzoic acid was studied by ¹H and ¹³C NMR, using S-INEPT, COSY, COLOC, and ROSEY methods, with the aid of model oligomers. Beside the expected N-benzoylated segments, the polymer also contained deacylated segments and about 50% of branching units. The polymer can be characterized as a statistical, highly branched copolymer of N-benzoyl-8-octanelactam and 8-octanelactam. © 1993 John Wiley & Sons, Inc.     

脑部磁共振结合静息态fMRI方法在卒中患者认知障碍中的应用

本研究主要探讨脑部磁共振结合静息态fMRI方法在卒中患者认知障碍中的应用。本研究将符合卒中认知障碍患者25例设为患者组,将25例健康者设为对照组。采用脑部静息态核磁共振对实验者进行扫描,以脑部双侧海马为种子点进行功能连接分析,并通过软件分析两组实验者静息态双侧海马差异。结果发现,与对照组相比,患者组右侧海马与左右侧额中回、左侧额下回等的连接减少;右侧海马与左侧颞上中回、双侧丘脑的连接增加;左侧海马与左侧颞额中回、右侧颞额上回、右侧额下回的连接减少;左侧海马与右侧顶下回连接增加。总之,本研究发现卒中患者海马脑区与颞叶皮层、额叶皮层之间的连接减少,可能是由卒中患者脑损害导致。     

Quantification of the velocity acceleration factor for colloidal transport in porous media using NMR

Nuclear magnetic resonance (NMR) techniques were used to quantify the transport of colloids through porous media. This was achieved via the application of chemically-resolved pulsed field gradient (PFG) methods, hence probing the displacement (probability distribution) propagators of both the colloidal and continuous liquid phase. A dilute decane-in-water emulsion was used with flow through a random glass sphere packing being considered. The acquired propagators allowed for quantification of both colloidal entrapment and the velocities of both the continuous phase and the flowing colloids. The flowing colloids were found to experience a velocity acceleration factor (VAF) increase of 1.08 relative to the continuous phase. This was found to be independent of displacement observation time or flowrate. It was speculated to be a consequence of radial exclusion due to the finite size of the colloids. Simulations of the colloidal transport were also performed using a lattice Boltzmann platform and a Lagrangian particle-tracking algorithm which incorporated colloidal radial exclusion. Reasonable agreement was observed between the simulation and the experimental data.     

A comparison of magnetic resonance imaging methods for fluid content imaging in porous media

Quantitative measurements are important for imaging fluid content in porous media. Conventional MRI methods suffer from contrast because of relaxation times in porous media, resulting in measurements of apparent fluid content, not the true fluid content. We compare four magnetic resonance imaging methods for fluid content imaging in several water‐saturated reservoir core plugs: frequency‐encoded spin echo, single point ramped imaging with T₁ enhancement, hybrid spin echo single point imaging (SE‐SPI), and T₂ mapping SE‐SPI. 1‐D profiles obtained with each method were compared in terms of image quality, image sensitivity, and quantification of water content. The image quality of short T₂ lifetime samples suffered from blurring in hybrid SE‐SPI images. Image sensitivity was the highest in the profiles obtained with frequency‐encoded spin echo. The quantification of frequency‐encoded spin echo, T₂ mapping SE‐SPI, and hybrid SE‐SPI suffered in core plugs with a significant population of short T₂ components because of T₂ attenuation. Overall, single point ramped imaging with T₁ enhancement was found to be the most general method for fluid content imaging. Copyright © 2013 John Wiley & Sons, Ltd.     

Molecular motion in nanocomposites of poly(ethylene oxide) and montmorillonite

Motion of chains of poly(ethylene oxide) within the interlayer spacing of 2:1 phyllosilicate/montmorillonite was studied with ¹H and ¹³C NMR spectroscopy. Measurements of the ¹H NMR line widths and relaxation times across a large temperature range were used to determine the effect of bulk thermal transitions on polymer chain motion within the nanocomposites. The results were consistent with previous reports of low apparent activation energies of motion. Details of the frequency and geometry of motion were obtained from a comparison of the ¹³C cross‐polarity/magic‐angle spinning spectra and relaxation times of the nanocomposite with those of the pure polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1678–1685, 2001     

Preparation and characterization of amino-functionalized magnetic nanogels via photopolymerization for MRI applications

To design peptide-targeted iron oxide as magnetic resonance imaging (MRI) contrast agents, amino-functionalized magnetic nanogels were prepared by using N-(2-aminoethyl) methacrylamide hydrochloride (AEM·HCl) as monomer via new photochemical approach. Their chemical structure and composition were characterized by Fourier transform infrared spectra (FTIR) and thermogravimetric analyses (TGA). The core–shell structure of magnetic nanogels was confirmed by high-resolution transmission electron microscopy (HRTEM). The good storage stability, high magnetic content (88.7%), high saturation magnetizations and superparamagnetic behavior suggested their great potentials as MRI contrast agents, which were confirmed by their measurements of r₂ and coronal image of the crossing of mouse kidney.     

NMR Characterization of Lanthanide(3+) Complexes of Tetraazatetrakisphosphinato and Tetraazatetra­kisphosphonato Ligands

The three‐dimensional structures in aqueous solution of the entire series of the Ln³⁺ complexes [Ln(DOTP*‐Et)]^? (formed from the free ligand P,P′,P″,P′′′‐[1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetrayltetrakis(methylene)]tetrakis[P‐ethylphosphinic acid] (H₄DOTP*‐Et) were studied by NMR techniques to rationalize the parameters governing the relaxivity of the Gd³⁺ complex and evaluate its potential as MRI contrast agent. From the ¹H‐ and ³¹P‐NMR lanthanide‐induced‐shift (LIS) values, especially of the [Yb(DOTP*‐Et)]^? complex, it was concluded that the [Ln(DOTP*‐Et)]^? complexes adopt in solution twisted square antiprismatic coordination geometries which change gradually their coordination‐cage structure along the lanthanide series. These complexes have no inner‐sphere‐H₂O coordination, and preferentially have the (R,R,R,R) configuration of the P‐atoms in the pendant arms. Self‐association was observed in aqueous solution for the tetraazatetrakisphosphonic acid ester complexes [Ln(DOTP*‐OEt)]^? (=[Ln(DOTP‐Et)]^?) and [Ln(DOTP*‐OBu)]^? (=[Ln(DOTP‐Bu)]^?) at and above 5 mM concentration, through analysis of ³¹P‐NMR, EPR, vapor‐pressure‐osmometry, and luminescence‐spectroscopic data. The presence of the cationic detergent cetylpyridinium chloride (CPC; but not of neutral surfactants) shifts the isomer equilibrium of [Eu(DOTP*‐OBu)]^? to the (S,S,S,S) form which selectively binds to the cationic micelle surface.     

Permanent Polymer Coating for in vivo MRI Visualization of Tissue Reinforcement Prostheses

The clinical advantage of MRI visualization of prostheses in soft tissue prolapses is very appealing as over 1 000 000 MRI‐transparent synthetic meshes are implanted annually, and postoperative complications such as mesh shrinkage and migration are frequent. Here, the synthesis of a new material composed of a DTPA‐Gd complex grafted onto a backbone of PMA via a covalent bond is described (DTPA‐Gd‐PMA). This new polymer is sprayed onto meshes and gives an MR signal for a long period without any significant release of Gd. In vitro cytocompatibility tests on fibroblasts show limited cytotoxicity. Microscopic investigations indicate that vital cells rapidly colonize the material. Finally, coated meshes implanted in rats are easily recognizable using an MR imaging system.

     

A comparison of the pseudo-steady-state and shrinking-core model for the reduction of titanium dioxide to titanium

A multistage shrinking-core model is proposed for the electrodeoxidation of titanium dioxide to titanium. This takes place through a series of steps from TiO₂ to Ti₃O₅ to Ti₂O₃ to TiO to Ti. Ideally, the model would incorporate a number of shells of the above lower oxide phases with the shrinking core of TiO₂ in the center but this would be mathematically intractable. A simpler method would be to use the shrinking-core model for each of the individual reductions. Taking the experimental parameters and diffusion coefficient of oxygen in the different phases into account, an analytical solution is developed for the transient differential equation. The first ten eigenvalues are taken into account for the computation of the series solution. This is then compared with a solution based on a pseudo-steady-state approximation to the transient equations. Based on the results, for higher values (>0.01) of dimensionless applied current density, I _d , both the solutions disagree in terms of the time it takes for the core to shrink completely. The difference appears to be decreasing with lower values of I _d but for larger values of I _d the pseudo-steady-state approximation fails to yield results close to the analytical solution.     

Multiple‐Frequency and Variable‐Temperature EPR Study of Gadolinium(III) Complexes with Polyaminocarboxylates: Analysis and Comparison of the Magnetically Dilute Powder and the Frozen‐Solution Spectra

An electron paramagnetic resonance (EPR) study of glasses and magnetically dilute powders of [Gd(DTPA)(H₂O)]^2?, [Gd(DOTA)(H₂O)]^?, and macromolecular gadolinate(1?) complexes P792 was carried out at the X‐ and Q‐bands and at 240 GHz (DTPA=diethylenetriaminepentaacetato; DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetato). The results show that the zero‐field splitting (ZFS) parameters for these complexes are quite different in a powder as compared to the frozen aqueous solution. In several complexes, an inversion of the sign of the axial component D of the zero field splitting is observed, indicating a significant structural change. In contrary to what was expected, powder samples obtained by lyophilization do not allow a more precise determination of the static ZFS parameters. The results obtained in glasses are more relevant to the problem of electron spin relaxation in aqueous solution than those obtained from powders.     

A Use of Modified Cyclodextrins as a Transporter for a Radiolabeled Tracer NMR Investigation

Cyclodextrins (D. Duchêne (ed.): New Trends in Cyclodextrins and Derivatives (1991)) have long been shown to be capable of modifying the water solubility of a number of hydrophobic guests through the formation of inclusion complexes. Among the three natural cyclodextrins (α, β and γ-cyclodextrins containing 6, 7 and 8 d-glucopyranose units, respectively), β-cyclodextrin is by far the most commonly used although it exhibits a weaker solubility in water (and therefore a weaker solubilization power). This specific feature has encouraged the synthesis of derivatives exhibiting an increased solubility in water. Methylated cyclodextrins are amongst the simplest derivatives, and their properties regarding the solubility and the solubilization power for hydrophobic guests are well documented especially concerning Heptakis (2,6-di-Omethyl)-cyclodextrin (DIMEB) and Heptakis (2,3,6-tri-Omethyl)-cyclodextrin (TRIMEB) K. Koizumi et al.:J. Chromatogr. 368, 329–337 (1986). In order to avoid the use of human serum albumin (HSA), this property has been applied here to the solubilization of a very sparingly water-soluble fatty acid derivative (16-iodo-3-methylhexadecanoic acid), which is known to localise in viable myocardial cells, allowing the generation of functional images reflecting the viability of the cardiac tissue through the use of radiolabeled analog (Demaison et al.: J. Nucl-Med. 29, 1230–1236 (1998)). Nuclear magnetic resonance (NMR) was used throughout this study to evidence that the observed solubilization and stabilisation (under conditions required for sterilisation) induced by cyclodextrins are due to the formation of a true inclusion complex and not to non-specific interactions; This technique further allows to derive thermodynamic as well as structural informations for this complex. On one hand, the inclusion complex prevents thermal degradation during sterilisation process compared to HSA. On the other hand, NMR displacement experiments against HSA showed that the complex likely dissociates in vivo.     

Structure determinations of nitrogen compounds with the aid of NQR, NMR, and ESCA spectroscopy

Since it is often necessary or desirable to determine the structures of compounds containing nitrogen directly via the nitrogen atoms, the nuclear quadrupole resonance (NQR) and the nuclear magnetic resonance (NMR) as well as the photoelectron and the Auger-electron spectroscopy (ESCA) of nitrogen are becoming increasingly important. A comparative review of these three methods on the basis of measurement effect, information obtainable, applications, and limitations forms the subject of this article.     

Assessment of the Extent of Starch Dissolution in Dimethyl Sulfoxide by 1H NMR Spectroscopy

Complete dissolution is needed for the separation, characterization, or homogeneous labeling of whole starch molecules. A method is presented to quantify the extent of starch dissolution in DMSO for the first time; it is validated on a commercial rice starch. It is used directly on starch dispersions containing possible undissolved or co‐dissolved species. High‐amylose maize starches, known to be digested slowly in vivo, only quantitatively dissolve in the presence of high concentrations of an H‐bond disrupter, LiBr, although they form clear dispersions at low LiBr concentrations. Starch quantitatively dissolves from waxy rice flours; non‐starch components partially co‐dissolve but do not interfere with the dissolution quantification.

     

NMR study of the propagation center in cationic polymerization of N-benzoyl-8-octanelactam. I. The structure of model living oligomers

Model living oligomers of N-benzoyl-8-octanelactam initiated by the model octanoylium hexachloroantimonate, SbCl₅, and by Ph₃C⁺ AsF₆^?, were studied by ¹H and ¹³C one- and two-dimensional nuclear magnetic resonance using the COSY, S-INEPT, COLOC, and ROESY methods. If prepared in the more solvating mixture of 1,1,2,2-tetrachloroethane (TCE) with 1,2-dichlorobenzene, the oligomers were found to be linear with the acylium ion as a living group on one end; in TCE only, the oligomers are highly branched. In both cases, the propagation center appears to be strongly coordinated to the nearest benzoylamide chain group. © 1993 John Wiley & Sons, Inc.     

基于MRI的绝经后女性腰椎退行性病变程度与骨质疏松的相关性研究

本研究探讨基于磁共振成像(MRI)的绝经后女性腰椎退行性病变程度与骨质疏松的关系。选取经骨密度检查确诊的骨质疏松绝经后女性患者50例为骨质疏松组、非骨质疏松症绝经后妇女50例作为对照组,两组妇女均接受MRI检查。结果显示,骨质疏松组的L1/L2、L2/L3、L3/L4、L4/L5、L1~S1椎间盘Pfirrmann分级评分均高于对照组,差异均具有统计学意义(P<0.05);骨质疏松组患者的腰椎L1/L2、L2/L3、L3/L4、L4/L5、L1~S1之间的BMD与椎间盘Pfirrmann分级评分呈显著的正相关关系(P<0.05);多元线性回归模型结果显示:绝经时间、年龄、腰椎BMD值与患者椎间盘Pfirrmann分级评分呈显著的正相关关系(P<0.05)。绝经后女性采用MRI检查评估的腰椎退行性病变程度Pfirrmann分级评分与骨质疏松程度有关,同时与患者的年龄、绝经时间长度有关。     

Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose Therein

The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The ¹H- and ¹³C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d₆, D₂O, CD₃OD, and CDCl₃). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %).     

Synthesis and relaxivity of polyamide paramagnetic metal complexes for magnetic resonance imaging

A new class of paramagnetic macromolecular magnetic resonance imaging contrast agents has been developed. Eight new polyamide ligands were synthesized by copolymerization of ethylenediaminetetraacetic acid dianhydride or diethylenetriaminepentaacetic acid dianhydride and diamine monomers. Their gadolinium(III), manganese(II) and iron(III) complexes were also synthesized. All polyamide ligands and metal complexes were characterized by ¹H nuclear magnetic resonance, infrared spectra and elemental analyses. Relaxivity studies showed that the polyamide paramagnetic metal complexes had obviously higher relaxation effectiveness as compared to corresponding simple monomeric paramagnetic metal complexes.     

3D-CE-TOF-SPGR对静脉性颅神经血管压迫综合征的应用

探讨3D-CE-TOF-SPGR序列在诊断静脉性颅神经血管压迫综合征中的临床应用价值。研究对象为我院收治的经手术证实且行磁共振断层血管成像(MRTA)检查的198例中7例静脉性颅神经血管压迫综合征患者,并与微血管减压术(MVD)中所见进行对照,其中原发性三叉神经痛5例、面肌痉挛2例。MRTA包括3D-FIESTA、3D-TOF-SPGR和3D-CE-TOF-SPGR序列,颅神经受压与责任静脉血管3D-FIESTA序列显示1例、3D-TOF-SPGR序列显示1例、3D-CE-TOF-SPGR序列显示6例,独立应用3D-CE-TOF-SPGR序列显示能力最佳(6/7,85.71%)。因此,MRTA成像技术中,3D-CE-TOF-SPGR序列能清楚显示目标颅神经及相应颅神经受压的静脉性责任血管,对指导临床MVD手术具有重要价值。