NMR imaging studies of coal

The permeation, transportation and swelling behavior of solvents into coal are investigated by NMR imaging using pyridine-ds and acetone-d6. Images of coal swollen with deuterated solvents illuminate proton distributions of mobile phases within the coal macromolecular networks. More information about the chemical and physical structure of coal can be obtained using NMR imaging techniques.     

2D NMR Investigation of Dynamic Equilibrium of Tautomers of Gossypol

Gossypol was obtained as an yellow platelike crystal with m.p. 210-214o . In CDCl3 there were three tautomers of gossypol: I aldehyde, II lactol,III ketal , in equilibrium .Their total H 1 NMR spectra were assigned by means of 1D and 2D NMR techniques including 1H-1H cosy , DEPT , HMQC (1H Detected Heteronuclear Multiple Quantum Coherence) and HMBC (1H Detected Heteronuclear Multiple Bond Connectivity) experiments . This paper first reported that we took use of the 2D NMR t…     

SPE–NMR metabolite sub-profiling of urine

NMR-based metabolite profiling of urine is a fast and reproducible method for detection of numerous metabolites with diverse chemical properties. However, signal overlap in the (1)H NMR profiles of human urine may hamper quantification and identification of metabolites. Therefore, a new method has been developed using automated solid-phase extraction (SPE) combined with NMR metabolite profiling. SPE-NMR of urine resulted in three fractions with complementary and reproducible sub-profiles. The sub-profile from the wash fraction (100?% water) contained polar metabolites; that from the first eluted fraction (10?% methanol-90?% water) semi-polar metabolites; and that from the second eluted fraction (100?% methanol) aromatic metabolites. The method was validated by analysis of urine samples collected from a crossover human nutritional intervention trial in which healthy volunteers consumed capsules containing a polyphenol-rich mixture of red wine and grape juice extract (WGM), the same polyphenol mixture dissolved in a soy drink (WGM_Soy), or a placebo (PLA), over a period of five days. Consumption of WGM clearly increased urinary excretion of 4-hydroxyhippuric acid, hippuric acid, 3-hydroxyphenylacetic acid, homovanillic acid, and 3-(3-hydroxyphenyl)-3-hydroxypropionic acid. However, there was no difference between the excreted amounts of these metabolites after consumption of WGM or WGM_Soy, indicating that the soy drink is a suitable carrier for WGM polyphenols. Interestingly, WGM_Soy induced a significant increase in excretion of cis-aconitate compared with WGM and PLA, suggesting a higher demand on the tricarboxylic acid cycle. In conclusion, SPE-NMR metabolite sub-profiling is a reliable and improved method for quantification and identification of metabolites in urine to discover dietary effects and markers of phytochemical exposure.     

The Characterization of Comblike Polymer Electrolyte by Means of NMR

Polymer solid electrolytes are a class of solid materials whose properties lie betweenthose of solids and liquids, and they have been widely used in energy resources,. metallurgy, environmental protection, electro-chemistry device and so on' '2.Inoue had pointed out that polystyrene derivative with many poly (ethylene oxide)PEO side chain could make conductivity reach 10-' S/cm. They think that the flexibilityo f the backbone is not necessarily the impoFtant factor to achieve a high conducti…     

NMR Microscopy of an “Anisotropic” Polymer

Two different samples of high-density polyethylene (HDPE) have been studied. One (isotropic) is extracted from the material core whereas the other (anisotropic) involves two sides which have been in contact with the injection mold. It is observed by NMR microscopy (using radiofrequency field gradients) that these two sides favor toluene penetration into the material. The distribution of toluene nuclear spin relaxation times (extracted from proton T₁ and T₂ images) exhibits likewise important differences between the two samples. These differences can be accounted for by partial molecular ordering at the vicinity of the “mold sides”. Finally, in investigating the anisotropic sample (without solvent), three different phases (two amorphous and one crystalline) are revealed by ¹³C chemical shift imaging experiments (performed with radiofrequency field gradients under CP/MAS conditions). Each amorphous component is preferentially present at one of the two “mold sides”.     

Study of association of alcohols in aprotic solvents by multinuclear NMR

Binary mixtures of alcohols(ethyl,n-butyl and n-amyl)with several aprotic sol-vents,such as acetone,dioxane,THF,DMSO and DMF have been studied systematically by~1H,~(13)C,~(15)N and ~(17)O NMR measurements.The concentration dependence of chemical shift ofthe solvent was used to evaluate equilibrium constants of the complexation of alcohols withthe solvents.A relationship between the proton shift of alcohol uncombined with the solventand its concentration was found,and the fraction of unassociated hydroxyl groups was thusquantitatively described.The effect of solvent on self association and complexation of thealcohol is discussed on the basis of the electron donicity of the solvents.     

NMR Study of the Inclusion Complexes of Carboxy-Phenoxathiin Derivatives with β-Cyclodextrin

The inclusion complexes of the carboxylate forms of 3-carboxy-(I) and 2-carboxy-phenoxathiin (II) with -cyclodextrin were studied by bothone- and two-dimensional NMR spectroscopy. The analysis of the induced chemical shifts of theguests in the presence of different amounts of the host indicates the formation of complexes with 1:1stoichiometry and association averaged pK values of 3.75 (I) and 4.4 (II). Thequalitative analysis of cross peaks in the ROESY spectra support the inclusion of the guests in the cavitywith the substituted phenyl ring, the COO^- group being in the proximity of the primary rim.     

Sol-Gel transition of κ-Carrageenan as viewed through NMR

²³Na, ⁸⁷Rb, and ¹³³Cs NMR spectra were observed to study an interaction between these cations and κ-carrageenan. It was found that the NMR intensity of gel-forming cations undergoes a remarkable change in the vicinity of the sol-gel transition temperature, while the non-gel-forming cation which coexists together with a gel-forming cation does not show any change. These results suggest that gel-forming cations selectively interact with κ-carrageenan.Motion of water molecules in the gel and the solution of κ-carrageenan was studied by measuring the water proton spin-spin relaxation time. The results indicate three different types of water molecule: a free bulk water molecule, a water molecule strongly bound to κ-carrageenan, and a water molecule weakly bound to the gel network.     

Formation and NMR study of some cyclic β-ketodithioacetals

An efficient method has been found for the preparation of cyclic monodithioacetats of 1,3-dicarbonyl compounds using boron trifluoride etherate as the acid catalyst. Asymmetric 1,3-diketones react regioselectively in most of the cases tried. A study of the ¹³C and ¹H nmr characteristics of these compounds has been carried out.     

NMR studies of conformations and molecular recognition of pyridinio-appended and nicotinamide-appended β-cyclodextrin

Abstract

The conformations of pyridinio-appended β-cyclodextrin (CDP⁺) and nicotinamide-appended β-cyclodextrin (CDNA⁺) were studied by NMR spectroscopy. The orientations of the pyridine residue of CDP⁺ and the nicotinamide residue of CDNA⁺ were determined by using a combination of NMR spectroscopic techniques. NMR spectra indicate that the shapes of the cavities of CDP⁺ and CDNA⁺ were changed after forming complexes. This change depended on the shape of the guest. CDNA⁺ could separate the ¹H resonances at the Cβ position of racemic tryptophan into two sets of resonances for each enantiomer.     

Determination of configurational–isomeric composition of synthetic isoprene rubbers using NMR spectroscopy

Production pieces of synthetic isoprene rubbers are studied using the nuclear magnetic resonance spectroscopy method. The measurements are performed by ¹Н and ¹³С NMR spectroscopy with variation of the conditions of sample preparation and taking and processing of spectra, which allows improving the accuracy of quantitative analysis of the content of monomer units characterized by different configurations.     

X-Ray Diffraction and NMR Study of Inclusion Complex of Podophyllotoxin with β-Cyclodextrin

Podophyllotoxin(Figurel)isalignan,naturallyoccurringinrootsandrhizomesofPodophyllumemodiWall.var.ChineseSprague'.Thiscompoundisclinicallyusedtotreatseveraltypesofcancer2.However,asadrug,itisrestraintedduetoitshightoxicityandsideeffecttohumanbody.Wehavepreparedtheinclusioncomplexofpodophyllotoxinwith0-cyclodextrin(Figure2)inordertodecreasetoxicityandincreasesolubilityofpodophyllotoxin.ThestrUctureoftheinclusioncomplexofthepodophyllotoxinwith0-cyclodextrinhavebeenstudiedbythemethodsofX-raydi…     

Solid State NMR and Fluorescence Studies of Conjugated Polymer Nanocomposties

^13C spin-lattice relaxation times （T1） of a conjugated polymer MEH-PPV in polymer/ layered silicate nanocomposites together with the steady state fluorescence emission and transient fluorescence decay measurements have been investigated. The T1 values of the conjugated carbons decrease dramatically according to the reduction of polymer concentration in the nano composites, while the fluorescence life times （τ） show a linear prolonging tendency. The results are explained from the point of view of molecular dynamics.     

^1H NMR Study of Polyvinylalcohol Irradiated by Ultra-violet

The effect of Ultra-violet light on the structure and motion of the polyvinyl alcohol (PVA) chains was studied by IH NMR, spin-lattice relaxation and IR spectroscopy. The results indicated that with the increase of irradiation time, the intensity of the polymer hydroxyl proton peaks decreased and finally vanished, which suggested the self-condensation between the hydroxyl groups proceeded. No methyl proton peaks appeared in the spectra after irradiation shows that there is no cleavage of polymer chain. The longer the irradiation time is, the wider the proton peak of the residual water of the solvent is and it shifted toward low field. This result implies that the hydrogen bonds formed between the polymer and the residual water. The absorption peak of hydroxyl group of the polymer moves toward the lower wave number in the IR spectrum that showed the existence of the hydrogen bonds between the PVA macromolecules.     

Unleashing the Potential of 17O NMR Spectroscopy Using Mechanochemistry

¹⁷O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen-17, ¹⁷O labeling is generally a prerequisite. This is a real obstacle for most research groups, because of the high costs and/or strong experimental constraints of the most frequently used ¹⁷O-labeling schemes. Here, we show for the first time that mechanosynthesis offers unique opportunities for enriching in ¹⁷O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user-friendly, and low-cost, which makes them highly attractive for a broad research community, and their suitability for ¹⁷O solid-state NMR applications is demonstrated.     

1H and 13C NMR characteristics of β-blockers

The β-blockers are important drugs and decades of clinical experience proved their high medical status. However, to the best of our knowledge, there is no complete assignment of (1)H and (13)C NMR resonances of popular representatives: acebutolol, alpenolol, pindolol, timolol and propranolol and the published NMR data on carvedilol and atenolol are incorrect. Therefore, (1)H and (13)C NMR spectroscopy was applied for the characterization of a series of β-adrenolytics: carvedilol (1), pindolol (2), alprenolol (3), acebutolol (4), atenolol (5), propranolol (6) and timolol (7). Two-dimensional NMR experiments (COSY, HMQC, HMBC, NOESY) allowed the unequivocal assignment of (1)H and (13)C spectra for solution (DMSO-d(6) ). Salts and bases can be easily distinguished based on (13)C chemical shifts which are within 65.0-65.5 ppm (OC2) and 46.9-47.0 (NC3) for hydrochlorides and larger, ca. 68.4 ppm (OC2) and 50.3-52.6 (NC3) for bases. NMR data of 1-7 should be included in pharmacopoeias.     

Hammett constants and NMR shifts of α-acyloxy carboxamide derivatives

Geometrical structures, Hammett constants, ¹H and ¹³C chemical shift values, molecular electrostatic potential maps, and several thermodynamic parameters of α-acyloxy carboxamide derivatives (4a–o) were calculated using HF and DFT/B3LYP methods with 6-31G(d) basis set. The optimized structures were compared with analogous compound. The ¹H and ¹³C NMR shielding tensors were computed with the Gauge-Independent Atomic Orbital (GIAO) method. Comparison of the experimental ¹H and ¹³C NMR chemical shifts of 4a–o molecules with the theoretical data indicates good agreement.     

Complex formation of fenchone with α-cyclodextrin: NMR titrations

¹³C NMR titration studies of inclusion complexes of bicyclic terpenoid, fenchone enantiomers with α-cyclodextrin revealed their 1:2 guest–host stoichiometry. Sequential binding constants were determined indicating a strong binding cooperativity of two α-cyclodextrin to fenchone. The overall association constants were used to calculate the Gibbs free energies of diastereomeric complex formation, which might be used as a measure of chiral recognition of fenchone by α-cyclodextrin. These results were compared with corresponding data derived for camphor, which is an isomeric bicyclic terpenoid.     

NMR double resonance study of azide binding to cytochrome c

Equilibrium constants for the binding of azide to ferri-cytochrome c at temperature rangeof 305—325 K were determined at pH=7 by using ~1H double resonance method.Thermodynamicvalues(⊿H~o=-34.5 kJ/mol,⊿S~o=-100 J/mol)were obtained from van't Hoff's relation andwere compared with those for azide binding to other ferric hemeproteins.The reason of loweraffinity of cytochrome c for azide was discussed.     

NMR characterization of α- and β-mannopyranurono-2,6-lactones

Determining the stereochemistry at the anomeric position of glycosides is imperative in chemical synthesis. As for 1,2-cis-β-glycosides such as β-mannosides, ¹³C-¹H coupling constants, ¹J_CHs, are conventionally used when glycosides are in an ordinary chair conformation. In this work, we searched for appropriate criteria to determine the stereochemistry of products in a recently developed glycosylation reaction using 2,6-lactones. As a result, we found that α-glycosides exhibited vicinal coupling constants of around 3.0?Hz?at the anomeric proton, as well as a long-range coupling between protons at C-1 and C-5, whereas β-glycosides had coupling constants of 1.2?Hz?at most. These figures are expected to be useful for future assignments. In addition, the observations obtained from this study revealed the conformation of glycosides with a 2,6-lactone moiety.