洗涤剂中含磷化合物的31PNMR快速检测方法

收集了常见的31种含磷无机化合物和84种含磷有机化合物,首次建立了含磷化合物的核磁共振谱图库,并以此为依据建立了31P NMR技术快速检测洗涤剂中含磷化合物的方法.对洗衣粉、金属清洗剂和除油剂样品进行31P NMR分析,经与31P谱图库比对,可快速确定含磷化合物的结构.结果表明,10种洗衣粉中仅有1种检出含磷化合物,其...     

^31P NMR Studies on the Ligand Dissociation of Trinuclear Molybde-num Cluster Compounds

A series of carboxylate-substituted trinudear molybdenum dus-ter compounds formulated as Mo3S4(DTP)3(RCO2)(L), where RffiH, CH3, C2H5, CH2Cl, CCl3, R^1C6H4(R^1 is the group on the benzene ring of aromatic carboxylate ), L=pyridine,CH3CN, DMF, have been synthesized by the ligand substitu-tion reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by ^31p NMR. The dissocia-tion process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution struc-ture and reactive properties of the duster. The long-distance in-teraction between ligands RCO2 and L is transported by Mo3S4 core.     

Determination of 31P,31P coupling constants in cyclotriphosphazenes and their influence on 1H and 13C NMR spectra of phosphorus substituents

¹H and ¹³C NMR spectra of symmetrically substituted cyclotriphosphazenes exhibit second‐order effects. The influence of the ³¹P,³¹P coupling constants between ring phosphorus atoms on these effects was studied. Some values of this coupling constant between phosphorus bearing identical substituents were measured using ¹³C satellites of the ³¹P signals or by introduction of a chiral substituent on the third phosphorus atom. Copyright © 2003 John Wiley & Sons, Ltd.     

Simultaneous determination of phenolic compounds and triterpenic acids in oregano growing wild in Greece by 31P NMR spectroscopy

³¹P nuclear magnetic resonance (NMR) spectroscopy was used to detect and quantify simultaneously a large number of phenolic compounds and the two triterpenic acids, ursolic acid and oleanolic acid, extracted from two oregano species Origanum onites and Origanum vulgare ssp. Hirtum using two different organic solvents ethanol and ethyl acetate. This analytical method is based on the derivatization of the hydroxyl and carboxyl groups of these compounds with the phosphorous reagent 2‐chloro‐4,4,5,5‐tetramethyl‐1,3,2‐dioxa phospholane and the identification of the phosphitylated compounds on the basis of the ³¹P chemical shifts. Unambiguous assignment of the ³¹P NMR chemical shifts of the dihydroxy‐ and polyhydroxy‐phenols in oregano species as well as those of the triterpenic acids was achieved upon comparison with the chemical shifts of model compounds assigned by using two‐dimensional NMR techniques. Furthermore, the integration of the appropriate signals of the hydroxyl derivatives in the corresponding ³¹P NMR spectra and the use of the phosphitylated cyclohexanol as an internal standard allowed the quantification of these compounds. The validity of this technique for quantitative measurements was thoroughly examined. Copyright © 2012 John Wiley & Sons, Ltd.     

骨髓增生异常综合症患者血液红细胞^31P—NMR谱的特征

本文介绍了用３１Ｐ－ＮＭＲ谱研究骨髓增生异常综合症（ＭＤＳ）患者血液红细胞的方法。分析了患者和正常人的血液红细胞在３１Ｐ－ＮＭＲ谱上的差异，探讨这些差异在临床医学上对ＭＤＳ患者进行诊断和疗效跟踪检测的应用途径。     

31P NMR assessment of the phosvitin-iron complex in mayonnaise

Lipid oxidation is the main reason for the limited shelf life of mayonnaise. One of the main catalysts of this process is iron, which is introduced in its ferric (Fe(III)) form via phosvitin, an egg yolk phosphoprotein rich in phosphoserines. The binding of Fe(III) to phosvitin and its ability to establish a redox couple with Fe(II) is believed to determine the oxidation rate of unsaturated lipids. In this work, a ³¹P NMR based method was developed to quantify loading of phosvitin with Fe(III) and its reductive release. Both features could be quantified in model phosvitin solutions by exploiting the paramagnetic broadening of ³¹P NMR signal of phosphoserine residues by Fe(III). This method was then successfully applied to quantify the phosvitin-Fe(III) loading in mayonnaise water phase by liquid NMR, whereas ³¹P NMR MAS could only provide a qualitative measure. The ³¹P NMR method showed a direct relation between loading of the Fe(III)-phosvitin complex and lipid oxidation.     

用31P NMR研究硫代磷酸酯水解反应历程

磷酸酯的水解反应是一类较为重要的反应,了解这类反应历程及机理对研究农药的毒性、环境保护、及指导农药的生产与合成具有十分重要的意义。~(31)PNMR灵敏度高,化学位移范围宽,偶合常数大.~(31)P NMR的化学位移对于分子中磷原子的价态、与磷原子直接相连的原子或基团的类型、数量、性质及构型的变化十分敏感.是研究有关含磷化合物结构问题的有效手段之一,因此本文采用~(31)P NMR方法研究了疏代磷酸酯的水解反应历程。本文所研究的化合物是一种新合成的含七元环的二硫代磷酸酯。其结构式如下:     

The Reaction Activity of Aromatic Carbonyl Compounds with Diphenylphosphine Oxide Studied by 31P NMR

Abstract

A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by ³¹P NMR spectroscopy.     

甲基氯化锡的核磁共振波谱研究

定性和定量测定甲基氯化锡,文献上报道的方法较多。有薄层色谱,气相色谱,极谱法等。但测定方法麻烦,重现性较差。我们采用核磁共振波谱的方法,利用溶剂化效应对化学位移的影响,分别定性定量测定了水溶液中的SnCl_4,(CH_3)_2SnCl_2和CH_3SnCl_3。并结合薄层分离和原子吸收分光光度法进行了比较,结果较为满意。     

Phosphorylated amino acids: model compounds for solid-state 31P NMR spectroscopic studies of proteins

Solid-state 31P NMR spectroscopy was applied to measure the isotropic chemical shifts, chemical shift anisotropies and asymmetry parameters of three phosphorylated amino acids, O-phospho-L-serine, O-phospho-L-threonine and O-phospho-L-tyrosine. The cross-polarization buildup rates and longitudinal relaxation times of 31P and 1H were-determined and compared with the values measured for a triphosphate (GppCH2p) bound to a crystalline protein (Ras). It is shown that the phosphorylated amino acids are well-suited model compounds, e.g. for the optimization of experiments on crystalline proteins. Two-dimensional exchange experiments on O-phospho-L-tyrosine indicate the existence of an exchange between the two different conformations of the molecule.     

Recent advances in computational 31P NMR: Part 1. Chemical shifts

This is the first part of two closely related reviews dealing with the computation of phosphorus-31 nuclear magnetic resonance chemical shifts in a wide series of organophosphorus compounds including complexes, clusters, and bioorganic phosphorus compounds. In particular, the analysis of the accuracy factors, such as substitution effects, solvent effects, vibrational corrections, and relativistic effects, is presented. This review is dedicated to the Full Member of the Russian Academy of Sciences Professor Boris A. Trofimov in view of his invaluable contribution to the field of synthesis, nuclear magnetic resonance, and computation studies of organophosphorus compounds.     

The Synthesis and 31P NMR Spectral Studies of Cyclophosphazenes

A modified method for preparing large-scale quantities of pure hexachlorocyclophosphazene (N₃P₃Cl₆) and octachlorocyclotetraphosphazene (N₄P₄Cl₈), phosphorus pentachloride with ammonium chloride, in the presence of zinc chloride, has been developed. The time of the reaction and the quantities of the catalyst are also studied. It is found that the optimum reaction time is 1.5 h and by-products are remarkably reduced by addition of 10% zinc chloride. As indicated by the ³¹ P NMR spectra, the synthesis and separation of cyclophosphazenes can be accomplished in moderate yield of tetramer (39%) and good yield of trimer (83%).     

31P NMR and HPLC Investigations of the Cyclophosphamide Metabolite,Phosphoramide Mustard

Abstract

Phosphoramide mustard (PM), a key active metabolite of the widely used anticancer drug cyclophosphamide (CP), can exist in several closely-related ionized, cyclized and substituted forms. We have developed a high pressure liquid chromatographic (HPLC) method for analysing serum concentrations of PM in order to relate these serum concentrations to toxicity and efficacy of treatment of CP. ³¹p NMR spectroscopy is used to verify the HPLC peak homology of the proposed PM peak.     

31P NMR spectroscopy in the quality control and authentication of extra-virgin olive oil: a review of recent progress

This review is a brief account on the application of a novel methodology to the quality control and authentication of extra-virgin olive oil. This methodology is based on the derivatization of the labile hydrogens of functional groups, such as hydroxyl and carboxyl groups, of olive oil constituents with the phosphorus reagent 2-chloro-4,4,5,5-tetramethyldioxaphospholane, and the use of the (31)P chemical shifts to identify the phosphitylated compounds. Various experimental aspects such as pertinent instrumentation, sample preparation, acquisition parameters and properties of the phosphorus reagent are reviewed. The strategy to assign the (31)P signals of the phosphitylated model compounds and olive oil constituents by employing 1D and 2D NMR experiments is presented. Finally, the capability of this technique to assess the quality and the genuineness of extra-virgin olive oil and to detect fraud is discussed.     

Solid‐state 31P NMR investigation on the status of guanine nucleotides in paclitaxel‐stabilized microtubules

Microtubule dynamics is a target for many chemotherapeutic drugs. In order to understand the biochemical effects of paclitaxel on the GTPase activity of tubulin, the status of guanine nucleotides in microtubules was investigated by ³¹P cross‐polarization magic angle spinning (CPMAS) NMR. Microtubules were freshly prepared in vitro in the presence of paclitaxel and then lyophilized in sucrose buffer for solid‐state NMR experiments. A ³¹P CPMAS NMR spectrum with the SNR of 25 was successfully acquired from the lyophilized microtubule sample. The broadness of the ³¹P spectral lines in the spectrum indicates that the molecular environments around the guanine nucleotides inside tubulin may not be as crystalline as reported by many diffraction studies. Deconvolution of the spectrum into four spectral components was carried out in comparison with the ³¹P NMR spectra obtained from five control samples. The spectral analysis suggested that about 13% of the nucleotides were present as GTP and 37% as GDP in the β‐tubulin (E‐site) of the microtubules. It was found that most of the GDPs were present as GDP‐P_i complex in the microtubules, which seems to be one of the effects of paclitaxel binding. Copyright © 2015 John Wiley & Sons, Ltd.     

31P Solid state NMR study of structure and chemical stability of dichlorotriphenylphosphorane

Solid state ³¹P NMR spectroscopy was used to examine, monitor and quantify the compound integrity of the chemical reagent dichlorotriphenylphosphorane. Comparison was also made with solution ³¹P NMR spectra which showed that this highly reactive species could be observed in dry benzene prior to conversion to the hydrolyzed product. This is the first reported solid state NMR study of the stability and reactivity of dichlorotriphenylphosphorane and the first account of its observation and comparison in the solution state. In the solid state, the ionic and covalent forms for dichlorotriphenylphosphorane were observed along with hydrolyzed products, however, the degree of hydrolysis was dependent upon the rotor packing conditions. Calculation of the relative percent composition of dichlorotriphenylphosphorane with hydrolyzed product was made for samples prepared in air versus under nitrogen atmosphere. This information was critical in adjusting the amount of reagent used in chemical development syntheses and scale up laboratories. All hydrolyzed products were identified, based upon chemical comparisons with spectra of pure materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Application of <Superscript>31</Superscript>P NMR for added polyphosphate determination in pork meat

Application of ³¹P NMR for qualitative and quantitative determination of added phosphorus compounds in meat samples is described. Furthermore, usefulness of the proposed method for monitoring of poly- and pyrophosphates hydrolysis in meat is discussed. Calibration curves based on the ³¹P resonance line areas were elaborated for Na₃P₃O₉, Na₅P₃O₁₀, Na₂H₂P₂O₇, and K₄P₂O₇ resulting in linearity (R ² = 0.9976, 0.9953, 0.9974, and 0.9524, respectively), detection limits (DL from 0.0018 mol L⁻¹ for Na₃P₃O₉ to 0.0070 mol L⁻¹ for K₄P₂O₇), and quantification limits (QL from 0.0060 mol L⁻¹ for Na₃P₃O₉ to 0.0234 mol L⁻¹ for K₄P₂O₇). The developed procedure was applied for laboratory prepared meat samples and compared with the standard UV-VIS method. The minimal sample pretreatment, obtained within-day precision (CV ≤ 2.0 %) and accuracy (as recovery ≥ 95 %) suggest ³¹P NMR as an alternative method of phosphorus determination in food analysis.     

31P NMR Studies of Diethyl Phosphite Derived Nanocrystalline Hydroxyapatite

³¹P nuclear magnetic resonance (NMR) spectroscopy was used to determine the structure of the intermediate species of sol derived from triethyl phosphite, calcium diethoxide and acetic acid. NMR spectral data revealed that the reaction proceeds via a dialkyl phosphite intermediate. The use of a dialkyl phosphite precursor (diethyl phosphite) with calcium diethoxide eliminated the aging time required in triethylphosphite method and offered an effective sol-gel procedure for monophasic hydroxyapatite.     

Monitoring of the insecticide trichlorfon by phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy

Trichlorfon is an organophosphorus insecticide, which is extensively being used for protection of fruit crops. Trichlorfon is a thermal labile compound, which cannot be easily determined by gas chromatography (GC) and has no suitable group for sensitive detection by high performance liquid chromatography (HPLC). In this study, a ³¹P nuclear magnetic resonance (³¹P NMR) has been described for monitoring of trichlorfon without any separation step. The quantitative works of ³¹P NMR spectroscopy has been performed in the presence of an internal standard (hexamethylphosphoramide). Limit of detection (LOD) for this method has been found to be 55 mg L⁻¹, without any sample preparation, and the linear working range was 150-5500 mg L⁻¹. Relative standard deviation (R.S.D.%) of the method for three replicates within and between days was obtained ≤9%. The average recovery efficiency was approximately 99-112%. This method was applied for monitoring trichlorfon in a commercial insecticide sample and tomato sample.     

Extraction processes reduce polyphosphate ion migration,dispersion and diffusion as detected with gel electrophoresis and 31P DOSY NMR

Inorganic polyphosphates (polyPs) have been identified in eukaryotic and prokaryotic cells alike. Various extraction methods have been optimized as a necessary step before identification and measurement of these polymers. Three commercially available sodium polyP glasses were either dissolved or dissolved and extracted by two commonly used polyP extraction techniques – perchloric acid or buffered phenol–chloroform. The products were separated by polyacrylamide gel electrophoresis (PAGE), stained with toluidine blue O, and the migration results quantitatively compared. Both extraction processes reduced the relative migration distances of the peak and leading edges, and the stained band lengths, suggesting reduced polyP migration and dispersion. ³¹P diffusion-ordered spectroscopy nuclear magnetic resonance confirmed that polyP extraction by perchloric acid or phenol–chloroform processes reduced polyP diffusion coefficients and suggested hydrolytic degradation with stronger end-chain signals. Reduced polyP diffusivity after extraction makes possible an overestimation of synthetic polyP chain length assignment when compared to unextracted polyP ladders with PAGE. The mechanism(s) for reduced synthetic polyP diffusion after extraction and intracellular chemical environment effects on migration are not known.