Nuclear magnetic resonance of paramagnetic metalloporphyrins

The present article reviews and discusses proton magnetic resonance studies on metalloporphyrins which provide good models for heme proteins in their physical and chemical properties. Emphasis is given on the discussion of the₁Hnmr work done in our laboratory.     

Nuclear magnetic resonance spectroscopic study on ionic liquids of 1-alkyl-3-methylimidazolium salts

Chemical shifts of ¹H and ¹³C NMR of series of methylimidazolium salts (MIM⁺, X=Br⁻, BF₄⁻ and PF₆⁻) function on the length of alkyl groups on the ring, type of solvents and the concentration. The bromides series demonstrate more chemical shift variation on H2 upon the change of solvents and concentration. Unexpected H-D exchange reactions were also observed in the MIM⁺Br⁻ by using CD₃OD and D₂O. The exchange rates strongly depend on the length of the alkyl group, which could cause more steric factor to reduce the interaction between deuterium atom from solvent and C2 of the ring.     

Aluminium ions at polyelectrolyte interfaces. II. Role in the surface-area-exclusion chromatography of humic acid

Surface-area-exclusion chromatography using Whatman glass microfibre filters modified by adsorption of aluminium ions as a stationary phase was used to evidence the different interfacial behaviour of aluminium ion complexed (tritium labelled) humic acids. Histograms with adsorption peaks, plateaux and humps on the stationary phase showed the various adsorption characteristics of the modified humic acid. The absence of adsorption for those constituents which were recovered in the effluent showed the very low degrees of complexation by aluminium ions to be responsible for the absence of interaction of the components with the stationary phase. Received: 24 July 2000  Accepted: 20 December 2000     

Nuclear magnetic resonance approaches to the rationalization of chromatographic enantiorecognition processes

NMR spectroscopy represents a valuable tool for obtaining information about structure and dynamics at a molecular level on the diastereoisomeric complexes formed by enantiomeric substrates and chromatographic chiral selectors or modifiers. Some examples collected from the literature show the potentialities of solution NMR spectroscopy in the rationalization of chromatographic enantiorecognition processes and the different NMR approaches needed according to the chiral selector features.     

Nuclear magnetic resonance relaxation studies of polyacrylamide solution

 The cohesive interaction among polymer chains in a polyacrylamide (PAAm)–D₂O solution has been studied by NMR relaxation. The NMR relaxation times of PAAm in the good solvent D₂O were measured at different temperatures. The results show that the solution system has a high local viscosity and that its relaxation characteristic is soft-solid-like. The temperature dependence of the relaxation behavior of the solution is obviously different from that of ordinary polymer solutions. The difference lies in the relaxation behavior of the methylene protons in the main chain of PAAm, as shown by analyzing the relaxation process with single exponential and biexponential decays. As the temperature increases, the solvation is weakened, leading polymer chains to form curling coils, thus hindering the movement of the methylene protons among the main chains. It can be expected from the existence of 80% fast-relaxing protons that there are a zhigh number of entanglements among the polymer chains in PAAm solution. The information about entanglements among the polymer chains can be deduced from the biexponential dependence of the spin–spin relaxation on the concentration of the polymer solutions. Received: 14 April 1999/Accepted in revised form: 12 October 1999     

Effect of pH and ionic strength on the interaction of humic acid with aluminium oxide

The effect of pH and neutral electrolyte on the interaction between humic acid/humate and γ-AlOOH (boehmite) was investigated. The quantitative characterization of surface charging for both partners was performed by means of potentiometric acid–base titration. The intrinsic equilibrium constants for surface charge formation were logK _a,1 ^int=6.7±0.2 and logK _a,2 ^int = 10.6±0.2 and the point of zero charge was 8.7±0.1 for aluminium oxide. The pH-dependent solubility and the speciation of dissolved aluminium was calculated (MINTEQA2). The fitted (FITEQL) pK values for dissociation of acidic groups of humic acid were pK ₁ = 3.7±0.1 and pK ₂ = 6.6±0.1 and the total acidity was 4.56 mmol g⁻¹. The pH range for the adsorption study was limited to between pH 5 and 10, where the amount of the aluminium species in the aqueous phase is negligible (less than 10⁻⁵ mol dm⁻³) and the complicating side equilibria can be neglected. Adsorption isotherms were determined at pH ∼ 5.5, ∼8.5 and ∼9.5, where the surface of adsorbent is positive, neutral and negative, respectively, and at 0.001, 0.1, 0.25 and 0.50 mol dm⁻³ NaNO₃. The isotherms are of the Langmuir type, except that measured at pH ∼ 5.5 in the presence of 0.25 and 0.5 mol dm⁻³ salt. The interaction between humic acid/humate and aluminium oxide is mainly a ligand-exchange reaction with humic macroions with changing conformation under the influence of the charged interface. With increasing ionic strength the surface complexation takes place with more and more compressed humic macroions. The contribution of Coulombic interaction of oppositely charged partners is significant at acidic pH. We suppose heterocoagulation of humic acid and aluminium oxide particles at pH ∼ 5.5 and higher salt content to explain the unusual increase in the apparent amount of humic acid adsorbed. Received: 20 July 1999 /Accepted in revised form: 20 October 1999     

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.     

Nuclear magnetic resonance study of Li and H diffusion in the high-temperature solid phase of LiBH4

In order to study the atomic jump motions in the high-temperature solid phase of LiBH₄, we have measured the ¹H and ¹¹B nuclear magnetic resonance (NMR) spectra and the ¹H, ⁷Li and ¹¹B spin–lattice relaxation rates in this compound over the resonance frequency range of 14–34.4 MHz. In the temperature range 384–500 K, all the spin–lattice relaxation data are satisfactorily described in terms of a thermally activated jump motion of Li ions with the pre-exponential factor τ₀=1.1×10⁻¹⁵ s and the activation energy E_a=0.56 eV. The observed frequency dependences of the spin–lattice relaxation rates in this temperature range exclude a presence of any distributions of the Li jump rate or any other jump processes on the frequency scale of 10⁷–10¹⁰ s⁻¹. The strong narrowing of the ¹H and ¹¹B NMR lines above 440 K is consistent with the onset of diffusive motion of the BH₄ tetrahedra.     

The role of variable surface charge and surface complexation in the adsorption of humic acid on magnetite

The ionic strength dependence of humic acid (HA) adsorption on magnetite (Fe₃O₄) was investigated at pH 5, 8 and 9, where variable charged magnetite is positive, neutral and negative, respectively. The adsorption studies revealed that HA has high affinity to magnetite surface especially at lower pH, where interacting partners have opposite charges. However, in spite of electrostatic repulsion at pH 9 notable amounts of humate are adsorbed. Increasing ionic strength enhances HA adsorption at each pH due to charge screening. The dominant interaction is probably a ligand-exchange reaction, nevertheless the Coulombic contribution to the organic matter accumulation on oxide surface is also significant under acidic condition. The results from size exclusion chromatography demonstrate that the smaller size HA fractions enriched with functional groups are adsorbed preferentially on the surface of magnetite at pH 8 in dilute NaCl solution.     

Characterisation of a synthesised fluorescent ligand (4-acridinol-1-sulphonic acid) using nuclear magnetic resonance spectroscopy

The synthesis and complete characterisation of the fluorescent ligand, 4-acridinol-1-sulphonic acid (the acridine analogue of 8-quinolinol-5-sulfonic acid) is described. Using a judicious array of nuclear magnetic resonance spectroscopy experiments, the structural elucidation and full assignment of all proton and carbon chemical shifts were afforded. The 4-acridinol-1-sulphonic acid was found to behave in a similar manner to 8-quinolinol-5-sulphonic acid, forming fluorescent complexes with magnesium(II) and zinc(II). The uncorrected emission maxima for the metal-acridinol complexes were found to be at around 620 nm compared to 505 nm for the respective quinolinol complexes. Unfortunately, preliminary spectrofluorimetric analytical figures of merit revealed that the detection limits of the new acridinol metal complexes were one and a half orders of magnitude poorer than those attained with the corresponding quinolinol ligand. However, in contrast to 8-quinolinol-5-sulphonic acid, the 4-acridinol-1-sulphonic acid ligand showed considerable selectivity for magnesium(II) and zinc(II) over aluminium(III).     

A rapid method for the detection of humic acid based on the poly(thymine)-templated copper nanoparticles

A label-free fluorescent method for sensitive detection of humic acid based on poly(thymine)-templated copper nanoparticles is reported.     

Combined use of liquid chromatography-nuclear magnetic resonance spectroscopy and liquid chromatography-mass spectrometry for the characterization of an acarbose degradation product

Directly coupled LC-MS and LC-NMR were applied to identify and structurally characterize an acarbose degradation product A in acidic media. A comparative analysis of the stop-flow LC-NMR (1H and TOCSY) and LC-MS data provided evidence that A is structurally related to acarbose, differing from the parent compound in a number of subunits present in the molecule. Spectral analysis revealed that A was the alpha-glucosidase inhibitor amylostatin XG. Complementary information obtained from the two methods led to the structural elucidation of A which was later corroborated by high-resolution NMR spectroscopy of the isolated molecule.     

Structures and magnetic properties of several novel lanthanide coordination polymers based on thiophene-2,5-dicarboxylic acid

Eight novel lanthanide complexes: {Ln(TDA)1.5(H2O)2}n (Ln = Pr(1a), Nd(2a)) and {Ln(TDA)(Ac)(H2O)}n (Ln = Pr(1), Nd(2), Eu(3), Gd(4), Tb(5), Dy(6); TDA = Thiophene-2,5-dicarboxylic acid anion) have been constructed by hydrothermal reaction. Structural analyses reveal that complexes 1a and 2a belong to the space group C2/c, exhibiting three-dimensional (3D) frameworks. Complexes 1-6 with P21/c space group were prepared in the presence of excessive ammonium acetate, giving rise to interesting 3D frameworks different from those of 1a and 2a. Magnetic property studies of 4-6 reveal the weak antiferromagnetic interaction exists between adjacent Gd3+ in 4. The complex 6 displays rather rare slow magnetization relaxation behavior in 3D frameworks.     

Nuclear magnetic resonance analysis of trace sulfur mustard chemicals in the environmental samples

Nuclear magnetic resonance （NMR） technique was used to screen and identify trace sulfur mustard chemicals in the organic and aqueous waste samples. 1H-NMR and one dimensional total correlation spectroscopy （1D TOCSY） were used for non-destructive screening analysis of the original samples. 1D TOCSY-TOCSY and 1D TOCSY incorporated with a chemical shift selective filter （1D CSSF-TOCSY） were applied in screening the contained sulfur mustard related compounds in the unknown samples. In order to meet the criteria for 1H-NMR data presentation, sample pretreatment technologies including liquid-liquid extraction, solvent exchange and solid phase extraction were used to eliminate the interference of the target resonances. Bis（2-chloroethyl） sulfide, 1, 3-Bis（vinylthio）propane and 1,3-Bis（2-hydroxyethylsulfonyl） propane were identified based on 1HNMR spectra comparison. The results were in good agreement with the list of spiking chemicals. The analytical strategies of this work can provide reference for the 1H-NMR analysis of the trace chemical warfare related compounds in official OPCW proficiency test. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Oxidative degradation of pentachlorophenol by an iron(III)-porphyrin catalyst bound to humic acid via formaldehyde polycondensation

Introduction of functional groups into humic substances is a novel trend in humic technology. In the present study, a biomimetic catalyst, 5-(p-hydroxyphenyl)-5,10,15,20-tetrasulfonatophenyl porphine iron(III) (FeTPPSOH), was introduced into humic acid via formaldehyde polycondensation. In the presence of KHSO₅, the self-degradation of the prepared catalysts, which were called “resol,” was retarded. In addition, the catalytic activity, which was evaluated by the percent pentachlorophenol (PCP) disappearance and levels of dechlorination, was significantly greater for the resol catalysts. The results of the present study show that resol catalysts effectively enhance oxidative degradation of PCP. The byproducts of oxidation were investigated by GC/MS analysis of n-hexane extracts of the reaction mixtures. This analysis demonstrated that another advantage of resol catalysts is that they prevent the formation of more harmful dimers, such as octachlorodibenzo-p-dioxin.     

Structural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) copolymer by nuclear magnetic resonance and mass spectrometry

Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have been combined to achieve the complete microstructural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) (PMAA-PMMA) copolymer synthesized by nitroxide-mediated polymerization. Various PMAA-PMMA species could be identified which mainly differ in terms of terminaisons. ¹H and ¹³C NMR experiments revealed the structure of the end-groups as well as the proportion of each co-monomer in the copolymers. These end-group masses were further confirmed from m/z values of doubly charged copolymer anions detected in the single stage mass spectrum. In contrast, copolymer composition derived from MS data was not consistent with NMR results, obviously due to strong mass bias well known to occur during electrospray ionization of these polymeric species. Tandem mass spectrometry could reveal the random nature of the copolymer based on typical dissociation reactions, i.e., water elimination occurred from any two contiguous MAA units while MAA-MMA pairs gave rise to the loss of a methanol molecule. Polymer backbone cleavages were also observed to occur and gave low abundance fragment ions which allowed the structure of the initiating end-group to be confirmed.     

Nuclear magnetic resonance studies of sulfur inversion in bis(cyclopentadienyl)-molybdenum and -tungsten complexes with dithioethers

The metallocene thioether derivatives [Cp₂M(MeSCH₂CH₂SMe)][PF₆]₂ (1, M = MO; 2, M = W), [Cp₂Mo(SCH₂CH₂SMe)][PF₆] (3) and [Cp₂M(SCH₂CH₂S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol⁻¹), 2 (51.2 ± 4.6 kJ mol⁻¹) and 3 (30.0 ± 3.1 kJ mol⁻¹). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour.     

Nuclear magnetic resonance studies of acetic acid inhibition of rec Zymomonas mobilis ZM4(pZB5)

The fermentation characteristics and effects of lignocelulosic toxic compounds on recombinant Zymomonas mobilis ZM4(pZB5), which is capable of converting both glucose and xylose to ethanol, and its parental strain, ZM4, were characterized using ¹³C and ³¹P nuclear magnetic resonance (NMR) in vivo. From the ³¹P NMR data, the levels of nucleoside triphosphates (NTP) of ZM(pZB5) using xylose were lower than those of glucose. This can be related to the intrinsically slower assimilation and/or metabolism of xylose compared to glucose and is evidence of a less energized state of ZM4(pZB5) cells during xylose fermentation. Acetic acid was shown to be strongly inhibitory to ZM4(pZB5) on xylose medium, with xylose utilization being completely inhibited at pH 5.0 or lower in the presence of 10.9 g/L of sodium acetate. From the ³¹P NMR results, the addition of sodium acetate caused decreased NTP and sugar phosphates, together with acidification of the cytoplasm. Intracellular deenergization and acidification appear to be the major mechanisms by which acetic acid exerts its toxic effects on this recombinant strain.     

Direct on-line hyphenation of capillary liquid chromatography to nuclear magnetic resonance spectroscopy: practical aspects and application to drug metabolite identification

In combining the high peak concentrations of capillary liquid chromatography (CapLC) with the high mass sensitivity of micro scale nuclear magnetic resonance (NMR) the hyphenation of CapLC to micro NMR offers a substantial gain in overall sensitivity. This paper deals with our experiences gained using a commercial CapLC-NMR system which has very recently become available. The limits of detection (SNR > 3) for a test compound of a molecular weight of M 318 were found to be approximately 100 ng (0.35 nmol) within an hour acquisition time and approximately 25 ng over night (85 pmol). Practical aspects such as the feasibility of stopped-flow experiments and sample handling issues are discussed in detail and first possible drug metabolite applications to hepatocyte incubations and direct analysis of plasma samples are presented.